WO2001068742A1

WO2001068742A1 - Process for producing polyimide

Info

Publication number: WO2001068742A1
Application number: PCT/JP2001/001938
Authority: WO
Inventors: Takashi Kuroki; Atsushi Shibuya; Shoji Tamai
Original assignee: Mitsui Chemicals, Inc.
Priority date: 2000-03-13
Filing date: 2001-03-13
Publication date: 2001-09-20
Also published as: US6916898B2; EP1273611A4; US20030158370A1; CN1164652C; KR20020081434A; EP1273611A1; CN1418234A; KR100503225B1; JP5246983B2

Abstract

A process for producing a polyimide which comprises subjecting a diamine and a tetracarboxylic dianhydride to imidization in a solvent comprising 50 to 100 wt.% composition consisting of a nitrogenous cyclic compound represented by the following chemical formula (1) and a phenol represented by the following chemical formula (2) in an equimolar proportion. (In the formula (1), X represents -CH2- or -N(CH3)-. In the formula (2), R1 and R2 may be same or different and each represents -H, -OH, -CH3, -C2H7, -C3H7, -C2H9, -C5H11, -C6H13, -C7H15, -C8H17, -C9H19, -C10H21, -OCH3, -O(C6H5), -NO2, -Cl, -Br, or -F.)

Description

Description Polyimide manufacturing method

The present invention relates to a method for producing a polyimide. More specifically, using an equimolar composition of a specific nitrogen-containing cyclic compound and a specific phenol as a solvent, an imidation reaction between diamine and tetracarboxylic dianhydride is performed. The present invention relates to a method for producing a polyimide by precipitating a polyimide and / or an oligomer to form a slurry into a reaction system.

The invention also relates to such an equimolar composition. Background art

Hitherto, polyimide has been widely used in various fields as a molding material, a composite material, an electric / electronic material, etc. because of its excellent heat resistance, mechanical properties, and electrical properties. In particular, biphenyltetracarboxylic acid-type polyimides have various characteristics different from pyromellitic acid-type polyimides, and are therefore highly useful, and have been studied and used in many applications. Among them, the following chemical formulas (4) to (6);

Since the polyimide having a repeating structural unit represented by is thermoplastic, it is possible to obtain molded articles of various shapes by melt molding such as press molding, extrusion molding, injection molding, etc., and its usefulness is extremely high ( GL Wilkes et al., Macromolecules, 30, pp.1012 (1997); S. Tamai et al., Polymer, 37 (16) pp.3683 (1996); S. Tamai et al., Polymer, 39 (10) pp.1945 (1998) etc.).

The polyimide molded body is usually manufactured by sinter molding of non-thermoplastic polyimide powder or melt molding of thermoplastic polyimide powder. Therefore, many methods for producing polyimide powder have been developed.

For example, Japanese Patent Application Laid-Open Nos. HEI 4-142332 and JP-A-2000-15545 disclose pyromellitic acid-type polyimides which can be heated and imidized in an aprotic polar solvent. A manufacturing method is disclosed. Pyromellitic acid-type polyimide has low solubility in a solvent, and the produced polyimide precipitates as the reaction proceeds, so that a polyimide powder can be easily obtained.

However, as shown in T. Nakano, 2nd Intern. Conf. On PI, etc., it was difficult to use the above method because biphenyltetracarboxylic acid type polyimide has high solubility in a solvent. In other words, even when imidized by heating in an aprotic polar solvent, the generated biphenyltetracarboxylic acid-type polyimide does not precipitate, or precipitates in a swollen state containing a large amount of solvent, thereby solidifying the reaction system. Such a problem arises.

For example, in GL Wilkes et al., Macromolecules, 30, pp. 1012 (1997), heat imidization in N-methyl-2-pyrrolidone, which is an aprotic polar solvent, yields the chemical formula (4) The polyimide which has a repeating structure represented by these is obtained. In this case, the produced polymer precipitates as the reaction proceeds, but the polymer concentration during the reaction is about 10% by weight. This is because the precipitated polyimide swells because it contains a large amount of solvent. This is because the system becomes clay-like and cannot be stirred.

Further, in JP-A-2000-108384, JP-A-08-213886, etc., by heating imidization in cresol, the chemical formula (4) or ( A polyimide having a repeating structure represented by 6) is obtained. In this case, since the produced polymer is dissolved in the solvent, a large amount of the poor solvent is used to precipitate the polymer after the reaction.

As mentioned above, the production of biphenyltetracarboxylic acid-type polyimides that are imidized by heating in a solvent is conventionally performed by a method that involves reacting at a low or high concentration and then diluting with a poor solvent. As a result, volumetric efficiency was extremely poor, and productivity was extremely low. That is, for example, when a reactor having a capacity of lm ³ is used, according to the method of GL Wilkes et al., The amount of polyimide obtained is less than 100 kg, According to the method disclosed in Japanese Patent Application Laid-Open No. 4 (1999) -1995, the amount of the obtained polyimide is less than 20 kg.

Furthermore, in the conventional method, since the precipitated polyimide contains a large amount of solvent, a great deal of effort has been paid to removing the solvent by drying or the like.

Japanese Patent Application Laid-Open No. 6-220194 discloses a method for directly imidizing an acid dianhydride and an aromatic diamine in an organic polar solvent, which is described in "Polyimide Solution Composition and Method for Producing the Same". A method for producing a polyimide characterized by performing polycondensation in the presence of a neutral compound ”.

The object of the present invention is a solution of an aliphatic-containing polyimide that is soluble in an organic polar solvent, and its object is to suppress a side reaction during imidization by heating in a solvent.

On the other hand, the method for producing a polyimide according to the present invention is intended to obtain a slurry-like reaction solution by precipitating the polyimide during the imidization reaction, and to obtain the polyimide simply by filtering the reaction solution as it is. And

Therefore, the subject of the invention or the purpose of the invention is significantly different from the above-mentioned publication.

In the above publication, the phenolic compound is used as a catalyst for suppressing side reactions, and the amount of the phenolic compound used is 0.1 to 0.5 times by weight (9 times the total solvent amount) with respect to the organic polar solvent. 333% by weight) as compared with the present invention. In addition, the method for producing biphenyltetracarboxylic acid-type polyimide with high productivity, which is clarified in the present invention, and among the organic polar solvents, the nitrogen-containing cyclic compound represented by the following chemical formula (1) is strongly different from phenols. Japanese Patent Application Laid-Open No. 6-220194 discloses that the polyimide precursor (polyamic acid) is dissolved, the polyimide is not dissolved, and that the equimolar composition has a remarkably high boiling point. Nothing is disclosed in the gazette. For example, the publication discloses that N-methyl-2-pyrrolidone as an example of a polar solvent and phenol (a mixture molar ratio of N-methyl-2-pyrrolidone / phenol is 65.5 / 34.5) are used as solvents. Describes that the synthesis of the polyimide contained in the above was carried out at a reaction temperature of 180, but mentions the specificity regarding the boiling point etc. of the mixed solvent consisting of N-methyl-2-pyrrolidone and phenols. There is no description that the mixed solvent has a high boiling point and is immiscible with water. The gazette also states that the use of an equimolar composition having such specific properties as a specific amount of solvent enables the precipitation of a biphenyltetracarboxylic acid-type polyimide during the imidization reaction. No suggestion.

From the above, there has been a demand for a highly productive method for producing biphenyltetracarboxylic acid-type polyimide.

In other words, the present invention is intended to solve the problems associated with the prior art as described above, and various properties of polyimide derived from various structures (such as moldability, sliding properties, low water absorption, and electrical properties). It is an object of the present invention to provide a method for obtaining polyimide by a simple, easy and inexpensive process without impairing thermal oxidation stability, radiation resistance, etc.). Disclosure of the invention

The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, when a specific composition is used as a reaction solvent, various physical properties of a biphenyltetracarboxylic acid-type polyimide (molding processability, It has been found that a polyimide can be obtained by a simple, easy and inexpensive process without impairing the sliding properties, low water absorption, electrical properties, thermal oxidation stability, radiation resistance, etc. Reached.

That is, the method for producing a polyimide according to the present invention includes a method represented by the following chemical formula (1). An equimolar composition of a nitrogen cyclic compound and a phenol represented by the following chemical formula (2)

The imidation reaction of diamines and tetracarboxylic dianhydride is carried out in a solvent containing 0 to 100% by weight.

(In the formula (l), X represents —CH ₂ — or one N (CH ₃ ) —. In the formula (2), R, and R ₂ may be the same or different from each other. -OH, - CH _3, -C2H7,

— C3I17, — C2ll9 C5llll, one. 6Π13, one 7Π one βΗΐ7, one CsHl9, one 1θΗ2! — 0CH3 0

, 1 Νθ2

Indicates any of _Cl, -Br or -F. ).

The tetracarboxylic dianhydride preferably contains biphenyltetracarboxylic dianhydride, and the tetracarboxylic dianhydride is biphenyltetracarboxylic dianhydride with respect to all tetracarboxylic dianhydrides. It is desirable to contain the acid dianhydride preferably in a proportion of 30 to 100 mol%.

The polyimide obtained by the imidization reaction preferably has a repeating structure represented by the following chemical formula (3).

(In Equation (3), Y is represented by at least one selected from the group consisting of Equations (e) and (h).)

(g)

(Where R may be the same or different from each other,

Single bond, — O— —CO— -S02-, — S—, — CH ₂ — or

-C (CH ₃ ) ₂ — ). The repeating structure represented by the chemical formula (3) is contained in a proportion of 30 to 100 mol% in all the repeating structures, and the remainder different from the repeating structure represented by the chemical formula (3) is 0 to 70 mol. % Is preferably contained.

The remainder preferably has a repeating structure composed of component units derived from aromatic tetracarboxylic acid, which is different from the repeating structure represented by the chemical formula (3). The repeating structure comprising the component units derived from the aromatic tetracarboxylic acid is preferably a repeating structure represented by the following chemical formulas (a) and Z or (b).

(In the formulas (a) and (b), the formulas (e) to (h)

Wherein, in the formulas (f), (g) and (h>, R may be the same or different from each other;

—〇, one CO—, one S〇 ₂ —, — S—, — CH ₂ — or one C (CH ₃ ) ₂ —.

In the above formula (b), Ar ₂ is at least selected from the group consisting of —O—, —CO—, one S〇 ₂ —, —S—, —CH ₂ — or one C (CH ₃ ) ₂ _ Represented by one. ). The polyimide having a repeating structure represented by the general formula (3) is a polyimide having at least one repeating structure represented by any of the following general formulas (4) to (6). Preferably _c

The compound represented by the chemical formula (1) is preferably N-methyl-2-pyrrolidone and / or 1,3′-dimethyl-2-imidazolidinone.

The phenols represented by the chemical formula (2) include phenol, 0-chloro phenol, m-clo phenol, p-chloro phenol, 0-cresol, m-cresolylile, P-cresol, 2,3 It is preferably at least one compound selected from the group consisting of -xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol .

A solvent containing an equimolar composition of the compound represented by the chemical formula (1) and the phenols represented by the chemical formula (2) in an amount of 50 to 100% by weight is the remainder of the solvent. Preferably, the compound represented by the chemical formula (1) or the phenols represented by the chemical formula (1) is contained in an amount of 0 to 50% by weight.

In the method for producing polyimide, the reaction system can be made into a slurry by precipitating polyimide and Z or an oligomer during the imidization reaction.

In the method for producing a polyimide, the reaction is preferably performed in the presence of a terminal blocking agent. According to the method for producing a polyimide, a product can be precipitated during an imidization reaction to obtain a polyimide powder.

The concentration of the starting monomers composed of diamines and tetracarboxylic dianhydride in the reaction solution ((total weight of starting monomers) / (total weight of starting monomers + weight of solvent)) is 5 to 50%. Preferably it is in the range of weight%.

The polyimide according to the present invention is obtained by the above method. The polyimide powder according to the present invention is obtained by the above method.

The solvent according to the present invention comprises an equimolar composition of a compound represented by the following chemical formula (1) and a phenol represented by the following chemical formula (2); (2)

(In the formula (1), X represents —CH ₂ — or —N (CH ₃ ) —. In the formula (2), R 1, and R ₂ may be the same or different from each other. , -OH, - C, -C2H7, - C 3 H 7, - C 2 ¾, -CsH, u - C 6 H 13, -C7H15, -C 8 Hi7, - C 9 H 19, -Cl, _0C, -0 (CeHs), -N (indicates either -k or -Br or -F).

When the solvent contains 50 to 100% by weight of an equimolar composition of the compound represented by the chemical formula (1) and the phenols represented by the chemical formula (2), Solvent may be contained. BRIEF DESCRIPTION OF THE FIGURES

FIG. A1 is a chart of the IR spectrum of N-methyl-2-pyrrolidone, m-cresol and their equimolar compositions.

FIG. A2 is a chart of ¹ H—NMR spectrum of an equimolar composition comprising N-methyl-2-pyrrolidone and m-cresol.

FIG. A3 is a chart of a ¹³ C-NMR spectrum of an equimolar composition comprising N-methyl-2-pyrrolidone and m-cresol.

Figure A4 shows N-methyl-2-pyrrolidone, P-chlorophenol and their equivalents. 3 is a chart of an IR spectrum of a molar composition.

FIG. A5 is a chart of the ¹ H—NMR spectrum of an equimolar composition comprising N-methyl-2-pyrrolidone and p-chlorophenol.

Figure A 6 are, N- methyl-2-pyrrolidone, P - equimolar set Narubutsu consisting black port phenol ^'3 is a C-NM R scan Bae Chiya one bets vector.

FIG. B1 is a chart of the IR spectrum of 1,3-dimethyl-2-imidazolidinone, m-cresol and their equimolar compositions.

FIG. B2 is a chart of ¹ H—NMR spectrum of an equimolar composition comprising 1,3-dimethyl-2-imidazolidinone and m-cresol.

FIG. B3 is a chart of ¹³ C—NMR spectrum of an equimolar composition comprising 1,3-dimethyl-2-imidazolidinone and m-cresol.

Figure B4 is a chart of the IR spectrum of 1,3-dimethyl-2-imidazolidinone, P-chlorophenol and their equimolar compositions.

FIG. B5 is a chart of ¹ H—NMR spectrum of an equimolar composition consisting of 1,3-dimethyl-2-imidazolidinone and p-chlorophenol.

Figure B 6 is 1,3-dimethyl-2-imidazolidinone, P - equimolar composition comprising black port phenols' is ³ C-NM R scan Bae Chiya one bets vector. BEST MODE FOR CARRYING OUT THE INVENTION

The present invention relates to a method for imidizing a compound containing 50 to 100% by weight of an equimolar composition of a nitrogen-containing cyclic compound represented by the chemical formula (1) and a phenol represented by the chemical formula (2). This is a method for producing polyimide. In this case, it can be preferably used for producing a polyimide having a repeating structure represented by the chemical formula (3).

Specific examples of the method for producing a polyimide of the present invention are shown below.

In a solvent containing 5.0 to 100% by weight of an equimolar composition of a nitrogen-containing cyclic compound represented by the chemical formula (1) and a phenol represented by the chemical formula (2), diamines and tetracarboxylic acid After dissolving or dispersing the anhydrides and the terminal blocking agent, the reaction system is heated to dissolve the monomer and the monomer or the polyimide precursor (polyamic acid) in the solvent, thereby making the reaction system uniform. Continue heating, diamines, tetracarboxylic acid By reacting and imidating the dianhydrides and the terminal capping agent, the resulting polyimide, Z or oligomer is precipitated in powder form, and the reaction system is made into a slurry. After completion of the reaction, the reaction solution is filtered to recover the powdered polyimide.

In the present invention, an equimolar composition of a nitrogen-containing cyclic compound represented by the chemical formula (1) and a phenol represented by the chemical formula (2) is used in an amount of 50 to 100 wt. This is a method for producing polyimide using a solvent containing 0.1% by weight.

(1) HO- (2)

In the above formula (1), X represents —CH ₂ — or _ N (CH ₃ ) —. In the above formula (2), RKR ₂ may be the same or different from each other. OH, -CH ₃ , -C2H7, — C ₃ H ₇ , -C2H9, -CsHiu -CeH, 3, -CiHis, -C ₈ Hi7, — C ₉ H _I9 , -C.0H2U — OCfk — 0 (C ₆ H ₅ ), -NO-Cl, -Br or -F.

Nitrogen-containing cyclic compound represented by chemical formula (1)>

The nitrogen-containing cyclic compound represented by the chemical formula (1) used in the present invention is N-methyl-2-pyrrolidone and Z or 1,3-dimethyl-2-imidazolidinone. The N-methyl-2-pyrrolidone according to the present invention can be prepared by appropriately utilizing a conventionally known method, for example, dehydrogenation of 1,4-butanediol or hydrogenation of maleic anhydride. Can be obtained by reacting α-butyrolactone obtained as described above with a monoalkylamine such as monomethylamine. N-methyl-pyrrolidone may be a commercially available product (manufactured by Mitsubishi Chemical Corporation, BASF, etc.).

The 1,3-dimethyl-2-imidazolidinone according to the present invention can be prepared by appropriately using a conventionally known method, or a commercially available product (such as a product of Mitsui Chemicals, Inc.) can be used. .

The nitrogen-containing cyclic compound represented by the chemical formula (1) is known as an aprotic polar solvent, and has conventionally been used as a polymerization solvent for polyimide. But However, these nitrogen-containing cyclic compounds have a high affinity for polyimide and easily dissolve polyimide. For this reason, in the conventional method for producing a polyimide using these nitrogen-containing cyclic compounds as a solvent, the produced polyimide does not precipitate and the reaction solution becomes viscous. Or a problem arises when the resulting polyimide precipitates in a swollen state containing a large amount of solvent and solidifies the reaction system.

Moreover, the nitrogen-containing cyclic compound represented by the chemical formula (1) has a high affinity for water and is arbitrarily mixed with water. Therefore, in the conventional method for producing a polyimide using these nitrogen-containing cyclic compounds as a solvent, it is difficult to remove water produced as a by-product from the solvent together with the production of the polyimide, resulting in a reduction in the reaction rate and the reached molecular weight. . Therefore, in a conventional method for producing a polyimide using these nitrogen-containing cyclic compounds as a solvent, a method of removing water by-produced by performing a reaction in the presence of a solvent azeotropic with water is common. there were.

Phenols represented by formula (2)>

As the phenols represented by the chemical formula (2) used in the present invention, specifically, for example, phenol, catechol, resorcinol, hydroquinone, 0-ethylphenol, m-ethylphenol, p-ethylphenol, octylphenol, 0-phenol Cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5_xylenol, guaiacol, nonylphenol , 0-chlorophenol, m-chlorophenol, p-chlorophenol, 0-bromophenol, m-bromophenol, P-bromophenol, 0-fluorophenol, m-fluorophenol, p-fluorophenol, 0 -Phenylphenol, m-phenylphenol, P-phenylphenol , 0-nitrophenol, m- nitrophenol, p- Nitorofue Nord, and the like. These may be used alone or in combination of two or more.

In the present invention, among such phenols,

Phenol, 0-cresol, m-cresol, P-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol Phenol, 3,5-xylenol, o-chlorophenol, m-chlorophenol, P-chlorophenol, etc. are preferably used. Of these, m-cresol, P-cresol and p-chlorophenol are preferred. Particularly preferably used.

In the present invention, such phenols can be used alone or in combination of two or more.

Such phenols can be prepared by appropriately utilizing a conventionally known method, and a commercially available phenol can be used.

The phenols represented by the chemical formula (2) are known as a good solvent for polyimide, and have been used as a polymerization solvent for polyimide. However, in the conventional method for producing polyimide using these phenols as a solvent, the produced polyimide does not precipitate and the reaction solution becomes viscous, and a large amount of poor solvent is required to recover the polyimide. There has been a problem that the resulting polyimide contains a large amount of solvent and precipitates in a swollen state, so that the reaction system is solidified.

Equimolar composition of the nitrogen-containing cyclic compound represented by the chemical formula (1) and the phenols represented by the chemical formula (2)>

The equimolar composition according to the present invention is a composition in which the nitrogen-containing cyclic compound represented by the chemical formula (1) and the phenols represented by the chemical formula (2) are mixed in an equimolar amount. The equimolar composition according to the present invention comprises a carbonyl group of the nitrogen-containing cyclic compound represented by the aforementioned chemical formula (1) and a phenol represented by the aforementioned chemical formula (2), as shown in Examples described later. The hydroxyl groups form strong hydrogen bonds and are tightly associated. Therefore, the affinity between the nitrogen-containing cyclic compound represented by the chemical formula (1) and the polyimide or between the phenols represented by the chemical formula (2) and the polyimide is relatively weakened, and as a result, It is considered that dissolution of the polyimide and swelling containing the solvent are suppressed.

In the equimolar composition according to the present invention, the nitrogen-containing cyclic compound represented by the chemical formula (1) and the phenols represented by the chemical formula (2) are strongly associated with each other. It has a high boiling point and is liquid at room temperature.

Specifically, as shown in the examples described later, for example, N-methyl An equimolar composition of le-2-pyrrolidone (boiling point 204, with a freezing point of 13-23) and m-cresol (boiling point 202.2, with a freezing point of 11.5) has a boiling point of 230 , A freezing point of O: less than, and an equimolar composition of N-methyl-2-pyrrolidone and p-cresol (boiling point: 21.9, freezing point: 34.8 :) has a boiling point of 245, Freezing point is less than 0. In the former case, the boiling point is about 15 to 20 T: higher than the boiling point of N-methyl-2-pyrrolidone and phenols, and in the latter example, it is about 40 to 45 T, which is extremely high. For example, the equimolar composition of 1,3-dimethyl-2-imidazolidinone (boiling point about 225, freezing point about 8) and m-cresol (boiling point about 202, freezing point about 12) In the case of a product, the boiling point is 237 :, freezing point is less than 0, and 1,3-dimethyl-2-imidazolidinone and P-chlorophenol are phenol (boiling point: about 217 :, freezing point: about 43) In the case of the equimolar composition, the boiling point is less than 257 and the freezing point is less than 0. In the former example, the boiling point of about 1,3-dimethyl-2-imidazolidinone is about 12 and the boiling point of m-cresol is 35, and in the latter example, 1,3-dimethyl-2- The boiling point is approximately 20 t: higher than the boiling point of imidazolidinone, and 28 higher than the boiling point of p-chlorophenol.

Thus, in the present invention, by mixing N-methyl-2-pyrrolidone and phenols in an equimolar amount, the boiling point is significantly increased, for example, by 1% from the boiling point of N-methyl-2-pyrrolidone or phenols. It is possible to obtain a composition having a freezing point of 0 or more, preferably 20 or more, more preferably 25 or more, and a liquid state at room temperature (for example, a liquid of 5). Also, by mixing 1,3-dimethyl-2-imidazolidinone and phenols in equimolar amounts, a remarkable increase in the boiling point occurs. For example, the boiling point of 1,3-dimethyl-2-imidazolidinone or phenols is increased by 3%. Or more, preferably at least 10 and more preferably at least 20 and particularly preferably at least 30 and a liquid having a freezing point of liquid at room temperature (for example, liquid at 5). Obtainable.

In the present invention, the boiling point of the solvent is obtained by measuring the liquidus temperature in the boiling solution and the gaseous phase temperature of the solvent vapor, and taking the temperature when these temperatures become the same. .

By the way, in general, the boiling point of a non-associative mixed solvent follows the Raoul's law, and the boiling point indicated by the Raoul's law depends on the interaction such as hydrogen bonding between the components of the mixed solvent. It is known to change. However, for example, the boiling point of an azeotropic composition mixture of phenol having weak acidity and aniline having weak basicity is 186.2, and the boiling point of phenol (at 181.2) and the boiling point of aniline (at 1 84.4), which is only slightly higher and does not show a remarkable increase in boiling point as in the present invention. Salts composed of an acid and a base are known to have a high melting point or non-volatility. For example, salts formed from weakly acidic phenols and sodium hydroxide (phenol sodium salt Hydrate) has a melting point of 61 to 64, and the salt formed from N-methyl-2-pyrrolidone (a), which exhibits weak basicity, has a melting point of 80 to 88. Because of its high melting point, it cannot be used as a solvent. From the above, the properties of the equimolar composition according to the present invention are extremely specific.

In the equimolar composition according to the present invention, the nitrogen-containing cyclic compound represented by the chemical formula (1) and the phenols represented by the chemical formula (2) are strongly associated by hydrogen bonding. Therefore, unlike a general azeotropic mixture, its composition does not depend on the pressure during the distillation operation and the like. The compositional ratio of such an equimolar composition according to the present invention hardly changes even if evaporation and concentration are repeated. Therefore, even if the equimolar composition according to the present invention is recovered and reused by distillation or the like, a constant composition can always be maintained, and thus no composition preparation is required. The equimolar composition according to the present invention separates into a nitrogen-containing cyclic compound represented by the chemical formula (1) and phenols in the presence of a base such as sodium hydroxide. The nitrogen-containing cyclic compound represented by the chemical formula (1) or phenols as the raw material can be recovered.

The equimolar composition according to the present invention has a high polarity and is immiscible with water, as shown in the examples described later. Therefore, it is excellent in solubility of raw materials and polyimide precursor (polyamic acid) at the time of polyimide production, and easily removes generated water at the time of dehydration reaction, and is suitable as a polyimide polymerization solvent. A solvent containing 50 to 100% by weight of an equimolar composition>

In the method for producing a polyimide of the present invention, an equimolar composition of the nitrogen-containing cyclic compound represented by the chemical formula (1) and the phenols represented by the chemical formula (2) is used as a reaction solvent in a range of 50 to 10. A solvent containing 0% by weight is used. The solvent in the present invention is mainly composed of the above equimolar composition, and the proportion of the equimolar composition in the total solvent weight is preferably 70 to 100% by weight, more preferably 80 to 1% by weight. Desirably, the content is 100% by weight, particularly preferably 90 to 100% by weight. The solvent is 0 to 50% by weight, preferably 0 to 30% by weight, more preferably 0 to 20% by weight, particularly preferably 0 to 10% by weight of the total solvent weight. May be included. The coexistence of another solvent can arbitrarily change various properties such as the melting point, boiling point, polarity, dielectric constant, and solubility of the reaction solvent used in the present invention.

Other solvents that may be included include, for example, phenol solvents, nonprotonic amide solvents, ether solvents, amine solvents, and the like.

As the phenolic solvent, the above-mentioned phenols (2) can be used. For example, phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-cresol, m-cresol, p-phenol —Cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol and the like. Examples of aprotic amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-getylacetamide, N_methyl-12-pyrrolidone, 1 , 3-dimethyl-12-imidazolidinone, N-methylcaprolactam, hexamethylphosphorotriamide, and the like. Examples of the ether solvents include 1,2-dimethoxyethane, bis (2-methoxyethoxy) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, and bis [2- (2-methoxy) Ethoxy) ethyl] ether and 1,4-dioxane.

Examples of the amine-based solvent include pyridine, quinoline, isoquinoline, picoline, j3-picoline, apicoline, isophorone, piperidine, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, Tripropylamine, tributylamine and the like.

In addition to the above, dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, sulfolane, diphenyl sulfone, tetramethyl urea, anisol, Water, benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, bromobenzene, o-dibromobenzene, m-dibromo Benzene, p-dibromobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, p-bromotoluene, acetone, methylethylketone, methylisobutylketone, methanol, Ethanol, propanol, isopropanol, butanol, isobutanol, pentane, hexane, heptane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, fluorobenzene, methyl acetate, ethyl acetate, butyl acetate, butyl acetate Methyl formate, ethyl formate It can be used.

In the method for producing a polyimide of the present invention, the solvent which may be contained is a nitrogen-containing cyclic compound represented by the chemical formula (1) or a chemical formula (2) constituting an equimolar composition used in the practice. It is particularly preferred that the same solvent as the phenols is used.

The method for producing a polyimide of the present invention can be preferably applied to the production of a polyimide having a repeating structure represented by the following formula (3).

In the above formula (3), Υ is represented by at least one selected from the group consisting of formulas (e) to (h).

Here, R may be the same or different from each other,

Single bond, — O—, —CO—, — S〇 ₂ —, — S—, — CH ₂ — or — C (CH ₃ ) ₂ —. Here, in the polyimide having a repeating structure represented by the chemical formula (3), the total amount of the repeating structure represented by the chemical formula (3) is 30 to 100 mol%, and preferably 50 to 100 mol%. Particularly preferably 55 to 100 mol%, and the balance is, for example, a compound having a repeating structure containing a component unit derived from an aromatic tetracarboxylic acid which is different from the repeating structure represented by the chemical formula (3). For example, it is desirable to contain a repeating structure represented by the following chemical formulas (a) and Z or (b) in an amount of 0 to 70 mol%, preferably 0 to 50 mol%, and particularly preferably 0 to 45 mol%.

(b)

In the above formulas (a) and (b), A is represented by at least one selected from the group consisting of formulas (e) and (h).

(g)

Here, Rs may be the same or different from each other, and are each a single bond, -0-, —CO—, — S〇 ₂ —, — S_, one CH ₂ — or — C (CH ₃ ) ₂ — Indicates one of

In the above formula (b), Ar ₂ is at least one selected from the group consisting of one O—, —CO—, —SO2-, —S—, one CH ₂ — or one C (CH ₃ ) ₂ — It is represented by

The polyimide having a repeating structure represented by the general formula (3) is a polyimide having at least one repeating structure represented by any of the following general formulas (4) to (6). Preferably an imide

It is preferable that the repeating structure constituting the remainder does not contain a component unit derived from an aliphatic tetracarboxylic acid having an aromatic ring or a fluorine-containing tetracarboxylic acid.

As shown in T. Nakano, 2nd Intern. Conf. On PI, etc., biphenyltetracarboxylic acid type polyimide having a repeating structure represented by the chemical formula (3) has high solubility in a solvent. Therefore, polyimide containing 30 to 100 mol% of the repeating structure represented by the chemical formula (3) in all the repeating structures is prepared by a conventional method, that is, N-methyl-2-pyrrolidone or cresol. When imidized by heating in a polar solvent, the generated polyimide does not precipitate, or precipitates in a swollen state containing a large amount of solvent, so that a problem may occur when the reaction system is solidified. In addition, polyimide having a repeating structure represented by the chemical formula (a) has low solubility in a solvent, and it is difficult to use a conventional method, i.e., when imidized by heating in a polar solvent such as N-methyl-2-pyrrolidone or cresol. In addition, since the produced polyimide is precipitated, the production method of the present invention is not required. Further, polyimide having a repeating structure represented by the chemical formula (b) has extremely high solubility in a solvent, Even when the production method is used, the produced polyimide does not precipitate or precipitates in a swollen state containing a large amount of solvent, so that a problem may occur when the reaction system solidifies.

The molecular end of the polyimide produced by the production method of the present invention may be sealed with a terminal blocking agent such as phthalic anhydride, aniline, maleic anhydride, and phenylethynyl phthalic anhydride. Further, it may have a branch in the main chain, side chain or terminal structure, and may have a structure for crosslinking, a cyclic structure, or the like. The degree of polymerization of the polyimide produced by the production method of the present invention is not limited, and can be arbitrarily selected according to the use of the polyimide. In the conventional method for producing polyimide, when the produced polyimide does not precipitate, that is, when the produced polyimide is dissolved in a solvent, the reaction solution becomes viscous, and the degree of polymerization of the produced polyimide is reduced. However, in the method for producing a polyimide of the present invention, the produced polyimide precipitates out and the reaction solution becomes a slurry, so that even when producing a high-molecular-weight polyimide, the reaction solution cannot be used. It does not become viscous enough to hinder stirring.

In the method for producing a polyimide of the present invention, conventionally known aromatic diamines can be preferably used. When aliphatic diamines, siloxane diamines, and fluorine-containing diamines are used, the obtained polyimide is dissolved in the solvent used in the present invention, and thus the desired effects of the present invention cannot be obtained. Sometimes. More specifically,

(1) Examples of diamines having one benzene ring include p-phenylenediamine and m-phenylenediamine.

(2) Examples of diamines having two benzene rings include:

3, 3'—diaminodiphenyl ether,

3, 4 '— diaminodiphenyl ether,

4, 4'-diaminodiphenyl ether,

3, 3'—diaminodiphenyl sulfide,

3, 4 'diaminodiphenyl sulfide, 4, 4 'diaminodiphenyl sulfide,

3, 3 'diaminodiphenyl sulfone,

3, 4 'diaminodiphenyl sulfone,

4, 4 'diaminodiphenyl sulfone,

3, 3 'Jamino Benzofuenonone,

4, 4 '— diaminobenzofunone,

3, 4 'Jamino Benzofunone,

3, 3 'diaminodiphenylmethane,

4, 4 'diaminodiphenylmethane,

3, 4 'diaminodiphenylmethane,

2, 2-di (3-aminophenyl) propane,

2, 2-di (4-aminophenyl) propane,

2- (3-aminophenyl) 1 2- (4-aminophenyl) propane,

1, 1-di (3-aminophenyl) 1 1-phenylene,

1, 1—di (4-aminophenyl) 1 1 _phenylenyl,

1- (3-aminophenyl) 1 1- (4-aminophenyl) 1 1-phenylethane

And the like.

(3) Diamines having three benzene rings include, for example,

1,3_bis (3-aminophenoxy) benzene,

1. 3-bis (4-aminophenoxy) benzene,

1. 4-bis (3-aminophenoxy) benzene,

1,4_bis (4-aminophenoxy) benzene,

1, 3-bis (3-aminobenzoyl) benzene,

1, 3-bis (4-aminobenzene) benzene,

1, 4-bis (3-aminobenzoyl) benzene,

1,4-bis (4-aminobenzoyl) benzene,

1,3-bis (3-amino-α, α-dimethylbenzyl) benzene,

1,3-bis (4-amino, α-dimethylbenzyl) benzene, 1, 4_bis (3-amino-a, a-dimethylbenzyl) benzene,

1,4-bis (4-amino-a, a-dimethylbenzyl) benzene,

2, 6_bis (3-aminophenoxy) benzonitrile,

2,6-bis (3-aminophenoxy) pyridine

And the like.

(4) Examples of diamines having four benzene rings include:

4, 4'-bis (3-aminophenoxy) biphenyl,

4, 4'-bis (4-aminophenoxy) biphenyl,

Bis [4- (3-aminophenoxy) phenyl] ketone,

Bis [4 -— (4-aminophenoxy) phenyl] ketone,

Bis [4 -— (3-aminophenoxy) phenyl] sulfide,

Bis [4- (4-aminophenoxy) phenyl] sulfide,

Bis [4 -— (3-aminophenoxy) phenyl] sulfone,

Bis [4- (4-aminophenoxy) phenyl] sulfone,

Bis [4 -— (3-aminophenoxy) phenyl] ether,

Bis [4 -— (4-aminophenoxy) phenyl] ether,

2,2_bis [4- (3-aminophenoxy) phenyl] propane,

2,2-bis [4- (4-aminophenyl) phenyl] propane, and the like.

(5) Diamines having five benzene rings include, for example,

1,3-bis [4- (3-aminophenoxy) benzoyl] benzene,

1,3-bis [4- (4-aminophenoxy) benzoyl] benzene,

1,4-bis [4- (3-aminophenoxy) benzoyl] benzene,

1,4-bis [4- (4-aminophenoxy) benzoyl] benzene,

1,3-bis [4- (3-aminophenoxy) -a, a-dimethylpenzyl] benzene,

1,3-bis [4- (4-aminophenoxy) — a, a-

, 4-bis [4-1- (3-aminophenoxy) HI, a- 4 _ bis [4 _ (4 _ aminophenoxy) aa and the like.

(6) Examples of diamines having six benzene rings include:

4,4,1-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether,

4,4,1-bis [4- (4-amino-, 1-dimethylbenzyl) phenoxy] benzophenone,

4,4,1-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone,

4,4,1-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone

And the like.

(7) Other diamines having an aromatic substituent include, for example,

3, 3'-diamino-1,4'-diphenoxybenzophenone,

3, 3 'diamino-4, 4' dibiphenoxybenzophenone,

3, 3'-diamino_4-phenoxybenzophenone,

3, 3 'diamino 4-biphenoxybenzophenone

And the like.

In the present invention, if necessary, part or all of the hydrogen atoms on the aromatic ring of the diamine having an aromatic ring may be replaced with a methyl group, a methoxy group, an ethynyl group serving as a crosslinking point, or benzocyclobutene. -Diamines substituted with a substituent such as a 4'-yl group, a vinyl group, an aryl group, a cyano group, an isocyanate group, a nitrile group or an isopropyl group can also be used.

Further, if necessary, diamines having a group such as a vinylene group, a vinylidene group or an ethynylidene group serving as a crosslinking point in a diamine main chain skeleton can be used.

Also, to introduce branching, triamines and tetraamines are used instead of diamines. Mines can also be used.

Such diamines can be used alone or in combination of two or more.

Tetracarboxylic dianhydride>

In the method for producing a polyimide according to the present invention, it is preferable to include biphenyltetracarboxylic dianhydride as the tetracarboxylic dianhydride. As such biphenyltetracarboxylic dianhydride, specifically, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenyltetracarboxylic acid Acid dianhydride; and 2,23,3, -biphenyltetracarboxylic dianhydride. These biphenyltetracarboxylic dianhydrides can be used alone or in combination of two or more. Among them, as the tetracarboxylic dianhydride in the present invention, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is particularly preferable.

In the present invention, biphenyltetracarboxylic dianhydride is preferably used as tetracarboxylic dianhydride, but other conventionally known tetracarboxylic dianhydrides are used together with biphenyltetracarboxylic dianhydride. be able to. As such another tetracarboxylic dianhydride, it is preferable to use an aromatic tetracarboxylic dianhydride. When an aliphatic tetracarboxylic acid containing no aromatic ring and a fluorine-containing tetracarboxylic acid are used, the obtained polyimide is dissolved in the solvent used in the present invention. May not be obtained. Examples of such aliphatic tetracarboxylic acids containing no aromatic ring include bicyclo (2,2,2) -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride. And ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride and the like.

Therefore, in the present invention, it is preferable not to use an aliphatic tetracarboxylic acid containing no aromatic ring or a fluorine-containing tetracarboxylic acid as another tetracarboxylic acid.

Other aromatic tetracarboxylic dianhydrides that can be used together with the biphenyltetracarboxylic dianhydride in the present invention include, for example, Pyromellitic dianhydride,

Bis (3,4-dicarboxyphenyl) ether dianhydride,

Bis (3,4-dicarboxyphenyl) sulfide dianhydride,

Bis (3,4-dicarboxyphenyl) sulfone dianhydride,

2,2-bis (3,4-dicarboxyphenyl) propane dianhydride,

1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride,

1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride,

4,4'-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride,

2,2-bis [(3,4-dicarboxyphenoxy) phenyl] propane dianhydride,

2, 3, 6, 7-naphthenetetracarboxylic dianhydride,

1,4,5,8-naphthylenetetracarboxylic dianhydride,

2, 2, 3, 3'-benzophenonetetracarboxylic dianhydride,

2, 3 ', 3, 4'-benzophenonetetracarboxylic dianhydride,

2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride,

Bis (2,3-dicarboxyphenyl) sulfide dianhydride,

Bis (2,3-dicarboxyphenyl) sulfone dianhydride,

1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride,

1,4-bis (2,3-dicarboxyphenoxy) benzene dianhydride, and

1,2,5,6_naphthylenetetracarboxylic dianhydride

And the like.

These other aromatic tetracarboxylic dianhydrides can be used alone or in combination of two or more.

In the present invention, if necessary, part or all of the hydrogen atoms on the aromatic ring of the aromatic tetracarboxylic dianhydride may be replaced with a methyl group, a methoxy group, an ethynyl group serving as a crosslinking point, or benzocyclobutene- A tetracarboxylic dianhydride substituted with a substituent such as a 4'-yl group, a vinyl group, an aryl group, a cyano group, an isocyanate group, a nitrile group, or an isopropenyl group can also be used. Further, tetracarboxylic dianhydride having a group such as a vinylene group, a vinylidene group, or an ethynylidene group serving as a crosslinking point in the main chain skeleton of the tetracarboxylic dianhydride can also be used.

In order to introduce a branch, hexacarboxylic acid trianhydrides and octacarboxylic acid tetraanhydrides can be used instead of tetracarboxylic dianhydride.

Such tetracarboxylic dianhydrides can be used alone or in combination of two or more.

The amount of tetracarboxylic dianhydride used in the present invention is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, of biphenyl tetracarboxylic dianhydride based on the total amount of tetracarboxylic dianhydride. 100 mol%, particularly preferably 55 to 100 mol%, and other tetracarboxylic dianhydrides are preferably 0 to 70 mol%, more preferably 0 to 50 mol%, Particularly preferably, the content is 0 to 45 mol%.

If the amount of the other tetracarboxylic dianhydride is more than 70 mol%, the solubility of the obtained polyimide in the solvent is very high, and even if the production method of the present invention is used, the produced polyimide will not In some cases, it does not precipitate, or it may precipitate in a swollen state containing a large amount of solvent, causing problems when the reaction system solidifies. Further, when pyromellitic dianhydride is used as more than 70 mol% as another tetracarboxylic dianhydride, the obtained polyimide has low solubility in a solvent. do not need.

That is, even in the conventional method of imidization by heating in a polar solvent such as N-methyl-2-pyrrolidone or cresol, the produced polyimide is precipitated.

The amount of the tetracarboxylic dianhydride used in the present invention (the sum of the amount of the biphenyltetracarboxylic dianhydride and the amount of the other tetracarboxylic dianhydride) is not particularly limited. It is preferable to use an amount of 0.8 to 1.25 mol per mol of the diamines. By changing the molar ratio of diamines and tetracarboxylic dianhydride used, the amount of polyimide The child quantity can be controlled.

When the molar ratio (tetracarboxylic dianhydride diamines) is less than 0.8, the polyimide molecular weight does not become a polyimide molecular weight capable of sufficiently exhibiting various properties of the polyimide. Even if it exceeds 25, the molecular weight of the polyimide may decrease.

In addition, when a monoamine is used as a terminal blocking agent as described later, the amount of tetracarboxylic dianhydride used is preferably 1.01 to 1.25 mol per 1 mol of diamines used. It is more preferably in the range of 1.05 to 1.20 mol, and particularly preferably in the range of 1.07 to 1.15 mol. In this case, if the molar ratio (tetracarboxylic dianhydride / diamines) is smaller than 1.01 or larger than 1.25, the end capping becomes insufficient, and the heat of the obtained polyimide becomes poor. Stability · May adversely affect processability.

When a dicarboxylic acid or an anhydride or derivative thereof described below is used as the terminal blocking agent, the amount of the tetracarboxylic dianhydride used is preferably 0.8 to 0.99 per mole of diamines. Mole, more preferably 0.85 to 0.97 mole, and particularly preferably in the range of 0.90 to 0.95. In this case, if the molar ratio (tetracarboxylic dianhydride Z diamines) is less than 0.8 or more than 0.99, the end capping becomes insufficient and the obtained polyimide Thermal stability · May adversely affect processability. The molecular weight of the polyimide can be controlled by changing the molar ratio of diamines and tetracarbonic dianhydride used in the production of the polyimide, and the purity and amount of the raw materials, the amount of impurities, the polymerization method, the type of solvent, and the polymerization. The optimum charging ratio may vary depending on the temperature, polymerization time, and the like.

In order to obtain a polyimide having a sufficiently high molecular weight, the molar ratio of diamines and tetracarboxylic dianhydrides to be used is preferably set to be approximately equimolar. In such a case, the viscosity of the reaction solution was remarkably increased by the conventional method in which the generated polyimide did not precipitate, and stirring was difficult. However, according to the production method of the present invention, the produced polyimide precipitates and the reaction system becomes a slurry, so that the reaction solution does not become viscous enough to hinder stirring. Terminal sealant>

In the method for producing a polyimide of the present invention, a terminal blocking agent can be used as necessary. The terminal blocking agent used is not particularly limited, and various types can be used. Among them, monoamines or dicarboxylic anhydrides can be preferably used.

Examples of the monoamine used as such a terminal blocking agent include aniline, ο-toluidine, m-toluidine, p_toluidine, 2,3-xylysine, 2,4-xylysine, 2,5-xylysine, 6-xylidine, 3,4-xylidine, 3,5-xylidine, o_chloroaniline, m-chloroaniline, p-chloroaniline, o-promorenyline, m-bromoaniline, p-bromoaniline Phosphorus, o-Nitroaline, m-Nitroaline, p-Nitroaline, o-anisidine, m-anisine, p-anisine, o-phenazine, m-phenetidine, p-phenetidine O-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehyde, o-aminobenzo Nitrile, m-aminobenzonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminophenylphenyl ether, 3-aminophenylphenyl ether, 4-aminophenylphenyl, 4-aminophenylphenyl ether 1 ter, 2-amino benzophenone, 3-amino benzophenone, 4-amino benzophenone, 2-amino phenyl sulfide, 3-amino phenyl sulfide, 4-amino phenyl sulfide 1, 2-aminophenylphenylsulfone, 3-aminophenylphenylsulfone, 4-aminophenylphenylsulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-naphthyl, 2- Amino 1 — Naphthol, 4 Amino 1 1 Naph! One, five—Amino one—Nuff! ^, 5-amino-2-naphthol, 7-amino-2-naphthol, 8-amino-1-naphthol, 8-amino-1-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9—Aminoanthracene, methylamine, dimethylamine, ethylamine, gel Cilamine, propylamine, dipropylamine, isopropylamine, disopropylamine, butylamine, dibutylamine, isoptylamine, disobutylamine, pentylamine, dipentylamine, benzylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexyl Xylamine and the like.

Examples of the dicarboxylic anhydride used as such a terminal capping agent include, for example, fluoric anhydride, 2,3-benzophenone dicarboxylic anhydride, and 3,4-benzophenone dicarboxylic anhydride. , 2,3-dicarboxyphenylphenyl ether anhydride, 3,4-dicarboxyphenylphenyl ether anhydride, 2,3-biphenyldicarboxylic anhydride, 3,4-biphenyldicarboxylic anhydride 2,3-dicarboxyphenyl phenyl sulfone anhydride, 3,4-dicarboxyphenyl phenyl sulfone anhydride, 2,3-dicarboxyphenyl phenyl sulfide anhydride, 3,4-di Carboxyphenyl sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 1,2-anthracene Dicarboxylic anhydride And 2,3-anthracene dicarboxylic anhydride, and 1,9-anthracene dicarboxylic anhydride.

These monoamines and dicarboxylic anhydrides may have a part of their structure substituted by a group having no reactivity with amine or carboxylic anhydride.

Further, a part of the structure of such a monoamine or dicarboxylic anhydride is converted into an ethynyl group, a benzocyclobutene-4'-yl group, a vinyl group, an aryl group, a cyano group, an isocyanate group, A monoamine or dicarboxylic anhydride substituted with a substituent such as a ditrilo group, an isopropenyl group, a vinylene group, a vinylidene group or an ethynylidene group can also be used.

Such terminal blocking agents can be used alone or in combination of two or more.

The amount of the terminal blocking agent used when using such a terminal blocking agent is not particularly limited,

[D a] (mol),

Total amount of tetracarboxylic dianhydride component (or its ring-opened products and derivatives) To [Tc] (mol),

The total amount of the monoamine component used as the terminal capping agent is [Ma] (mol), and the total amount of the dicarboxylic anhydride component (or the ring-opened product or derivative thereof) used as the terminal capping agent is [Dc] (mol). )

100≥ ([Dc] — [Ma]) / ([Da]-[Tc]) ≥2

It is preferably within the range of, more preferably,

20≥ ([Dc]-[Ma]) / ([Da]-[Tc]) ≥3

Is preferably within the range.

If the value of ([Dc] — [Ma]) / ([Da]-[Tc]) is less than 2, sufficient molecular end capping cannot be achieved, and the resulting polyimide will not have thermal stability and heat. Oxidation stability and moldability may deteriorate.

When the value of ([Dc] — [Ma]) / ([Da] — [Tc]) exceeds 100, it may be difficult to control the molecular weight of the obtained polyimide and to wash the surplus end-capping agent. In the production method of the present invention, the terminal blocking agent is preferably charged together with the aromatic diamine and the aromatic tetracarboxylic dianhydride at the start of the reaction. In the production method of the present invention, the generated polymer precipitates with the progress of the reaction, so that when the terminal blocking agent is added later, the terminal may not be sufficiently sealed. Catalysts>

In the method for producing a polyimide of the present invention, a known catalyst can be used in combination with the reaction of diamines and tetracarboxylic dianhydrides. When a catalyst is used in combination, it is preferable to use a base catalyst.

Examples of such a base catalyst include, for example,

Pyridine, quinoline, isoquinoline, hy-picoline, / 3-picoline, a-picolin, isophorone, piperidine, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine Amine compounds such as

Imidazole, N, N-dimethylaniline, N, N-Jetylaniline, etc. Organic base,

Inorganic bases such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, hydrogen carbonate carbonate, and sodium hydrogen carbonate.

The amount of the catalyst to be used is preferably 0.01 to 0.5 mol, more preferably 0.05 to 0.2 mol, per 1 mol of the diamines used. Production of polyimide

The method for producing a polyimide according to the present invention comprises 50 to 100% by weight of an equimolar composition of the nitrogen-containing cyclic compound represented by the chemical formula (1) and the phenol represented by the chemical formula (2). A solvent may be used, and there is no particular limitation, but the starting monomers diamines and tetracarboxylic dianhydrides are heated while dissolved or suspended in the solvent, and thermally heated. A method of performing dehydration imidization is preferable. At this time, the charging order and timing of the diamines, tetracarboxylic dianhydride and terminal blocking agent can be arbitrarily selected.

The concentration of the raw material monomers that can be used in the present invention is not particularly limited, and can be arbitrarily set depending on conditions such as the structure and molecular weight of the polyimide to be obtained, the reaction temperature, and the temperature at the time of filtration. In the production method according to the present invention, slurry polymerization at a higher concentration is possible as compared with a known production method by imidation with a phenol-based single solvent.

In order to make use of such characteristics according to the present invention, the concentration of the preferable raw material monomers based on the total weight of the reaction solution is 5 to 50% by weight, more preferably 10 to 45% by weight. Preferably it is 18 to 40% by weight, particularly preferably 23 to 37% by weight.

If the concentration of the raw material monomers is less than 5% by weight, the yield per batch may be reduced and the production efficiency may be deteriorated, so that the features of the present invention may be impaired. %, It may be difficult to stir the reaction solution during the imidization reaction, and stable production may be difficult.

The concentration is (total weight of raw material monomers) / {(total of raw material monomers) Weight) + (weight of solvent)} X refers to the concentration indicated by 100 (%).

The polymerization temperature, polymerization time and polymerization pressure are not particularly limited, and known conditions can be applied. That is, the reaction temperature is preferably 80 to about 400, and more preferably 100 to about 300. The upper limit of the reaction temperature is limited by the boiling point of the solvent under the pressure during the polymerization. Although the reaction time varies depending on the solvent used and other reaction conditions, it is generally preferable to carry out the reaction in the range of 0.5 to 24 hours.

In addition, in the production method according to the present invention, the solvent used for the reaction has a high boiling point, and the polymerization reaction can be efficiently performed even at a temperature exceeding, for example, 200. For this reason, the reaction pressure can be performed at normal pressure, and no special device is required for increasing or decreasing the pressure of the reaction system, and the process can be simplified. The polymerization reaction can be performed in any of air, nitrogen, helium, neon, and argon atmospheres, and the atmosphere during the reaction is not particularly limited. However, it is preferable to use an inert gas such as nitrogen or argon.

The concentration of the polyimide thus obtained relative to the total weight of the reaction solution is preferably 5 to 50% by weight, more preferably 10 to 45% by weight, and still more preferably 18 to 40% by weight. %, Particularly preferably 23 to 37% by weight.

The concentration refers to a concentration represented by (weight of polyimide) / {(weight of polyimide) + (weight of solvent)} × 100 (%). Reaction solution state during polymerization process>

In the method for producing a polyimide of the present invention, an equimolar composition of the nitrogen-containing cyclic compound represented by the chemical formula (1) and the phenol represented by the chemical formula (2) is used as a solvent in an amount of 50 to 100. The use of a solvent containing 5% by weight of polyimide allows the polyimide to precipitate in the solvent under the conditions of normal pressure and the above-mentioned reaction temperature range at the final stage of the imidization reaction in the polyimide production process according to the present invention. It can be in the form of a slurry. A typical reaction state is, for example, that the monomer and / or polyimide precursor are dissolved in the initial stage of the reaction, and the reaction solution is once a homogeneous solution. Then, as the reaction proceeds, polyimide precipitates, and the reaction solution becomes a slurry. In the present specification, the “end stage” of the reaction means a stage at which the reaction has proceeded as described above and the polymerization and imidization of the polyimide have almost been completed.

Even if such a slurry-like reaction solution is cooled to about room temperature, the reaction solution does not become a viscous state but remains in a slurry state.

In the present invention, a polyimide can be obtained by simply filtering the slurry-like reaction solution thus obtained as it is. To ensure more reliable polyimide deposition, toluene, methanol, ethanol, methyl ethyl ketone, water, N-methyl-2-pyrrolidone, or the like may be added as a poor solvent if necessary.

In the method for producing a polyimide of the present invention, the polyimide obtained by such an operation is usually in the form of a powder, so that the solvent can be easily removed and the polyimide can be easily used for various purposes. The solvent in the recovered polyimide can be removed by various known methods. For example, the solvent can be removed by drying at 100 to 400 in an oven.

Usually, in the production of polyimide, the polymerization reaction is often carried out at a somewhat lower raw material concentration (for example, about 10% by weight) in order to prevent solidification of the produced polymer, which varies depending on the structure of the produced polyimide. However, when the high boiling point mixed solvent according to the present invention is used, the reaction solution solidifies even when imidation is performed with the total concentration of the polyimide raw materials being higher (for example, 20% by weight or more). Therefore, the reaction solution can be obtained in a slurry state, so that the productivity of polyimide in an industrial process can be improved. Moreover, the obtained polyimide has the same physical properties as polyimide obtained by conventional low-concentration polymerization (for example, a concentration of about 10% by weight), and its moldability, sliding properties, low water absorption, and electrical properties Various physical properties such as thermal oxidation stability and radiation resistance are not impaired. The polyimide obtained by the polyimide production method of the present invention has the same physical properties as the polyimide obtained by the conventionally known method, The method can be applied to compression molding, sinter molding, extrusion molding, injection molding, transfer molding, and the like, and can be used for conventionally known applications. Industrial applicability

Polyimides obtained by the production method of the present invention include, for example, in the field of semiconductor containers, trays for IC packaging, trays for IC production processes, IC sockets, wafer carriers, etc.In the field of electric and electronic components, connectors, sockets, In addition to bobbins, hard disk carriers, LCD display carriers, jigs for manufacturing crystal oscillator manufacturing trays, etc.In the field of office equipment parts, separation claws for copiers, heat-insulated bearings for copiers, gears for copiers, etc. Thrust washers, transmission rings, piston rings, oil seal rings, etc. in the automotive parts field. Bearings, pump gears, conveyor chains, slide bushings for stretch machines, etc. in the industrial equipment parts field. Fiber etc. .

Further, the equimolar composition or the solvent containing a specific amount of the equimolar composition according to the present invention has a high boiling point and a low freezing point, and has an appropriate polarity (for example, a dielectric constant of 20 (similar to acetone)). ~ 33 (similar to methanol)) and has the unique property of being immiscible with water, so it can be used as an organic solvent under normal reaction conditions, It can be used conveniently. For example, various organic and inorganic reaction solvents, solvents for polyimide synthesis during the production of polymers such as polyimide, solvents for extracting and purifying various chemicals, solvents for dissolving inks such as dyes and pigments, solvents for paints, cleaning agents, Refrigerant, heat medium, polymer-soluble paint • Solvents for adhesives, polymer plasticizers, etc. Of these, for example, the production of polyimide may be carried out under a high temperature condition such as a polymerization temperature of 200 or more under normal pressure, and the equimolar composition according to the present invention or the equimolar composition is characterized. The solvent contained in a fixed amount is particularly useful as an organic solvent for polyimide synthesis. Furthermore, since such an equimolar composition according to the present invention or a solvent containing a specific amount of the equimolar composition has a high boiling point, when used as a solvent for polymerization or reaction, the reaction temperature is reduced. The reaction time can be shortened. Further, when a solvent containing a specific amount of the equimolar composition or the corresponding molar composition according to the present invention is used as a purification solvent, in a crystallization operation of dissolving at a high temperature and precipitating at a low temperature, the temperature difference between the high temperature and the low temperature is determined. By increasing the value, a large difference in solubility is obtained, so that the purification yield of the target product can be improved. The invention's effect

According to the method for producing a polyimide of the present invention, a slurry-like reaction solution in which the polyimide is precipitated can be obtained, and the polyimide can be obtained by simply filtering the reaction solution as it is, and thus the polyimide can be obtained by an easy and inexpensive process. Obtainable. Moreover, according to the production method of the present invention, even when the polymerization reaction is carried out at a high concentration of the polyimide production raw material, the reaction solution does not solidify and is in a slurry state, so that the productivity of polyimide is improved. It does not impair the various physical properties of polyimide derived from various structures (moldability, sliding properties, low water absorption, electrical properties, thermal oxidation stability, radiation resistance, etc.). Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by these Examples.

Test methods of various tests common to the examples and the comparative examples are shown below.

1) IR spectrum of equimolar composition

It was measured by a liquid membrane method using FTS-165 manufactured by Bio-Rad.

2) NMR spectrum of equimolar composition

The liquid composition was measured as it was using Unity Inova400 manufactured by Varian.

3) Dielectric constant (ε '), dielectric loss tangent (tan5) of equimolar composition

The measurement was performed by the LCR meter bridge method using a precision LCR meter HP4284A manufactured by Agilent Technologies and a measuring electrode LE-22 manufactured by Ando Electric. The measurement frequency is 1ΜΗζ, and the measurement conditions are 22 persons1 and Z60 ± 2% RH.

4) Logarithmic viscosity of polyimide powder

0.50 g of the sample was added to a mixed solvent of p-chlorophenol and phenol (90 : 10 weight ratio) After heating and dissolving in 100 ml, the measurement was carried out at 35.

5) Melt viscosity

Orifice 1. Omm (diameter) X I 0 mm (long), load 100 kgf, residence time 5 minutes unless otherwise specified, using a Shimadzu Koka type flow tester (CFT 500A).

6) 5% weight loss temperature

The measurement was carried out in air using DTA-TG (Shimadzu DT-40 series, 40 M) at a heating rate of 10 Zmin.

7) Glass transition temperature · Crystal melting temperature (melting point)

The temperature was measured with a DSC (Shimadzu DT-40 series, DSC-41M) at a heating rate of 10 / min. Example A 1

N-methyl-2-pyrrolidone is charged into a sufficiently dried flask with a packed column, rectified under a nitrogen atmosphere at normal pressure, and has a boiling point of 204.5 and a water content of l Oppm or less. -Methyl-2-pyrrolidone was prepared. In addition, m-cresol (special grade) was rectified in the same manner to prepare purified m-cresol having a boiling point of 202.2 t and a water content of 1 Oppm or less.

In a dry box, 99.1 g (1.OOmol) of the above purified N-methyl-2-pyrrolidone was charged into a flask, and while stirring, further purified 108.1 g (1.OOmol) of m-cresol. ) Was gradually added to obtain an equimolar composition (liquid) of purified N-methyl-2-pyrrolidone and purified m-cresol.

The obtained equimolar composition was heated at normal pressure, and the temperatures of the liquid phase and the gaseous phase at the time of boiling were 230. This is 25.5 higher than the boiling point of purified N-methyl-2-piperidone (204.5) and 27.81: higher than the boiling point of purified m-cresol (at 202.2). Met. Further, the obtained equimolar composition was placed in a flask and exposed to ice water at 0 for 3 hours, but the equimolar composition did not solidify and remained in a liquid state.

Obtained equimolar composition and reagent grade N-methyl-2-pyrrolidone, m-cresol Figure A1 shows the IR spectrum. Compared to those of N-methyl-2-pyrrolidone and m-cresol alone, the IR spectrum of the equimolar composition shows a broad band of 3000-4000 cm-j showing OH stretching vibration that forms intramolecular and intermolecular hydrogen bonds. And the band of 167 1 cm- ¹ which shows C = 0 stretching vibration is shifted low wave number. In addition, C-O stretching vibration due to the formation of aggregates by hydrogen bonding is observed at 1287 cm- ¹ . The above results indicate that C = O of N-methyl-2-pyrrolidone and OH of m-cresol form a strong hydrogen bond in the equimolar composition.

FIGS. A2 and A3 show ¹ H- and ¹³ C-NMR spectra of the obtained equimolar composition. The proton and carbon signals of the equimolar composition are equivalent to those of known N-methyl-2-pyrrolidone and m-cresol alone, indicating that no ionic bond is formed.

The obtained equimolar composition had a dielectric constant of 24.0 and a dielectric loss tangent of 0.353. In addition, 5 g of the obtained equimolar composition was mixed with 5 g of pure water in a sample bottle and stirred vigorously, but the equimolar composition and pure water were not mixed and remained in two layers. . Example A 2

40 g of the composition obtained in Example A1 was charged into a simple evaporative distillation apparatus equipped with a decompression device, a cooling pipe, an effluent receiver, and a thermometer, and into which nitrogen was introduced by a capillary. After the pressure in the system was reduced to 1.33 × 10 ⁴ Pa, the temperature was gradually raised from room temperature in an oil bath, and about 10 g of the distilled solution was fractionated in three times from the start of distillation.

The composition of the obtained first distillation, middle distillation, later distillation, and bottom residue (about 10 g each) was measured by gas chromatography (column: UniotrHP 80/100 KG-02, 3.2ΦΧ6ιη, column temperature 180). Each of the compositions was 組成 -methyl-2-pyrrolidone Zm-cresole = 47.8% by weight 52.2% by weight (1: 1 by molar ratio). No difference was seen. The calibration curve was created using the purified N-methyl-2-piperidone prepared in Example A1 and purified m-cresol. Example A 3

In Example A2, the internal pressure of the flask was 1.33 × 10 ⁴ Pa, Distillation was carried out in the same manner as in Example A2, except that the internal pressure of Rusco was set to 1.33 × 10 ³ Pa, to obtain about 10 g of each of the first distillation, the middle distillation, the last distillation, and the bottom. When the compositions of N-methyl-2-pyrrolidone and m-cresol contained therein were measured in the same manner as in Example A2, each composition was N-methyl-2-pyrrolidone m-cresol. = 47.8% by weight Z52.2% by weight (1: 1 by molar ratio), and no difference was found in the respective compositions. Example A 4

N-Methyl-2-pyrrolidone 100. Og (1. Olmol) and m-cresol 100.0 g (0.925mol) were precisely weighed, and a simple distillation apparatus equipped with a cooling tube, distillate receiver, and thermometer And subjected to simple evaporation distillation under a nitrogen atmosphere at normal pressure. After distilling off about 20 g of the first fraction, the temperature at the top of the column was stabilized at 230, and then the receiver was switched to another one and distillation was performed to obtain about 170 g of the main fraction. The composition of the obtained main fraction was N-methyl-2-pyrrolidone / m-cresol = 47.8% by weight 52.2% by weight (1: 1 by molar ratio). Example A 5

About 100 g of the main fraction obtained in Example A4 was charged into a flask equipped with a cooling tube and a distillate receiver, and was boiled at normal pressure under a nitrogen atmosphere. did. The recovered liquid was further boiled and recovered in the same manner. The composition of the obtained liquid was N-methyl-2-pyrrolidone Zm-cresol = 47.8% by weight 52.2% by weight (1: 1 by molar ratio). Example A6-8

The equimolar composition of purified N-methyl-2-pyrrolidone and purified m-cresol, obtained in Example A1, and purified N-methyl-2-pyrrolidone or purified m-cresol were used in amounts shown in Table 1. Was blended. Table 1 shows the boiling points measured in the same manner as in Example A1.

Each of the obtained solutions in Table 1 was placed in a flask and exposed to ice water of 0 for 3 hours, but the solution did not solidify and remained in a liquid state. Comparative Example A;

The equimolar composition of purified N-methyl-2-pyrrolidone and purified m-cresol obtained in Example A1, and purified N-methyl-2-pyrrolidone or purified m-cresol are shown in Table 1. It was blended in the amounts shown. Table 1 shows the boiling points measured in the same manner as in Example A1. Example A 9

p-Cresol (special grade) was rectified in the same manner as in Example A1, and purified P-cresol having a boiling point of 201.9 and a water content of 1 O ppm or less was prepared.

In a dry box, the purified N-methyl-2-pyrrolidone 99.1 (1.OOmol) prepared in Example A1 was charged into a flask and stirred, and further purified P-cresol 108.1 was added. g (1.0 OOmol) was gradually added to obtain an equimolar composition (liquid) of purified N-methyl-2-pyrrolidone and purified p-cresol.

The obtained equimolar composition was heated at normal pressure, and the temperatures of the liquid phase and the gaseous phase at the time of boiling were measured. This is 23.5 higher than the boiling point (at 204.5) of purified N-methyl-2-piperidone and higher than the boiling point (at 201.9) of purified P-cresol. The temperature was high at 26.1. Further, the obtained equimolar composition was placed in a flask and exposed to ice water at 0 for 3 hours, but the equimolar composition did not solidify and remained in a liquid state.

In addition, 5 g of the obtained equimolar composition was mixed with 5 g of pure water in a sample bottle and stirred vigorously, but the equimolar composition and pure water were not mixed and remained in two layers. Was. Example A 10

The p-cloguchi phenol (special grade) was rectified in the same manner as in Example A1 to prepare a purified P-cloguchi phenol having a boiling point of 2 17 and a water content of 1 O ppm or less.

In a dry box, 99.1 g (1.0 OOmol) of the purified N-methyl-2-pyrrolidone prepared in Example A1 was charged into a flask, and the mixture was further stirred and further purified. 28.6 g (1.OOmol) was gradually added to obtain an equimolar composition (liquid) of purified N-methyl-2-pyrrolidone and purified P-chlorophenol.

The equimolar composition obtained is heated at normal pressure and the temperature of the liquid and gaseous phases during boiling is measured. As a result, it was 245 for both the liquid phase and the gas phase. This was about 41 higher than the boiling point of purified N-methyl-2-piperidone (at 204.5) and 28 higher than the boiling point of purified p-chlorophenol (217). Further, the obtained equimolar composition was placed in a flask and exposed to ice water at 0 for 3 hours, but the equimolar composition did not solidify and remained in a liquid state.

FIG. A4 shows the IR spectra of the obtained equimolar composition and the reagent grade N-methyl-2-pyrrolidone and P-chlorophenol. Compared to those of N-methyl-2-pyrrolidone and P-chlorophenol alone, the IR spectrum of the equimolar composition shows OH stretching vibration that forms intramolecular and intermolecular hydrogen bonds. The band at 1671 cm- ¹ showing the C = 0 stretching vibration has a low wavenumber shift. In addition, C-O stretching vibration due to the formation of aggregates by hydrogen bonding is observed at 1269 cm- ¹ . The above results show that in the equimolar composition, C = 0 of N-methyl-2-pyrrolidone and OH of P-chlorophenol form a strong hydrogen bond.

¹ H- and ¹³ C-NMR spectra of the obtained equimolar composition are shown in FIGS. The proton and carbon signals of the equimolar composition were equivalent to those of known N-methyl-2-pyrrolidone and p-chlorophenol alone, indicating that no ionic bond was formed.

The obtained equimolar composition had a dielectric constant of 32.8 and a dielectric loss tangent of 0.434. In addition, 5 g of the obtained equimolar composition was mixed with 5 g of pure water in a sample bottle and stirred vigorously, but the equimolar composition and pure water were not mixed and remained in two layers. .

Table A

Equimolar composition: equimolar composition of purified N-methyl-2-pyrrolidone and purified m-cresol Content: equimolar composition amount (g) Total Z content (25 g) X100 (wt%) Example B 1

1,3-Dimethyl-2-imidazolidinone was charged into a fully-dried flask with a packed column, rectified under a nitrogen atmosphere at normal pressure, and had a boiling point of 22.5.5 and a water content of 10 ppm or less. Purification of 1,3-dimethyl-2-imidazolidinone was prepared. In addition, m-cresol (special grade) was rectified in the same manner to prepare purified m-cresol having a boiling point of 202.2 t and a water content of 10 ppm or less.

In a dry box, the above purified 1,3-dimethyl-2-imidazolidinone 1 14.1 g (l.OOmol) is charged into a flask, and while stirring, further purified m-cresol 108 .1 g (l.OOmol) was added to obtain an equimolar composition (liquid) of purified 1,3-dimethyl-2-imidazolidinone and purified m-cresol.

The obtained equimolar composition was heated at normal pressure, and the temperatures of the liquid phase and the gaseous phase at the time of boiling were measured. This is about 12 higher than the boiling point of purified 1,3-dimethyl-2-imidazolidinone (25.5 V) and about 3 higher than the boiling point of purified m-cresol (at 202.2). 5 was high temperature. Further, the obtained equimolar composition was placed in a flask and exposed to ice water at 0 for 3 hours, but the equimolar composition did not solidify and remained in a liquid state.

Fig. B1 shows the IR spectra of the obtained equimolar composition and reagent grade 1,3-dimethyl-2-imidazolidinone and m-cresol. Compared to 1,3-dimethyl-2-imidazolidinone and m-cresol alone, the IR spectrum of the equimolar composition shows OH stretching vibration that forms intramolecular and intermolecular hydrogen bonds. 0 0 cm one ^first broadband and C = 〇 stretching bands of vibration of 1 6 9 3 cm- 'indicated is lower wavenumber shift. The above results show that in the equimolar composition, C = 0 of 1,3-dimethyl-2-imidazolidinone and OH of m-cresol form a strong hydrogen bond.

The ¹ H- and ¹³ C-NMR spectra of the obtained equimolar composition are shown in FIGS. The proton and carbon signals of the equimolar composition are equivalent to those of known 1,3-dimethyl-2-imidazolidinone and m-cresol alone, indicating that no ionic bond has been formed.

The obtained equimolar composition had a dielectric constant of 24.1 and a dielectric loss tangent of 0.412. In addition, 5 g of the obtained equimolar composition was mixed with 5 g of pure water in a sample bottle and stirred vigorously, but the equimolar composition and pure water were not mixed and remained in two layers. . Example B 2

40 g of the composition obtained in Example B1 was charged into a simple evaporative distillation apparatus equipped with a decompression device, a cooling pipe, an effluent receiver, and a thermometer and into which nitrogen was introduced by a capillary. After reducing the pressure of the system to ^{1. 3 3 X 1 0 4} Pa, collected and gradually heated from room temperature in an oil bath, distilled solution from about 1 0 g Dzu', three times the distillate starts min did.

The composition of the obtained first fraction, middle fraction, tail fraction, and bottom residue (about 10 g each) was analyzed by gas chromatography (column: UniotrHP 80/100 KG-02, 3.2 Φ X 6 m, column temperature 180) As a result of the measurement, 1,3-dimethyl-2-imidazolidinone / m-cresol = 51.35% by weight / 48.65% by weight (1: 1 by molar ratio) ), And there was no difference between the compositions. The calibration curve was created using the purified 1,3-dimethyl-2-imidazolidinone prepared in Example B1 and purified m-cresol. Example B 3

In Example B2, distillation was performed in the same manner as in Example B2, except that the internal pressure of the flask was 1.33 × 10 ⁴ Pa, and the pressure was set to 1.33 × 10 ³ Pa. Approximately 10 g of each of the first, middle, late and kettles were obtained. The compositions of 1,3-dimethyl-2-imidazolidinone and m-cresol contained therein were measured in the same manner as in Example B2, and each of the compositions was 1,3-dimethyl- 2-imidazolidinone Zm-cresol = 51.35% by weight Z48.65% by weight (1: 1 by molar ratio), and no difference was observed between the respective compositions. Example B 4

100.0 g (0.876 mol) of 1,3-dimethyl-2-imidazolidinone and 100.0 g (0.925 mol) of m-cresol were precisely weighed and simple distillation equipped with a cooling tube, distillate receiver, and thermometer The apparatus was charged and subjected to simple evaporation distillation under a nitrogen atmosphere at normal pressure. About 30 g of first fraction After that, the overhead temperature was stabilized at 237, and then the receiver was switched to another receiver and distillation was carried out. The composition of the obtained main fraction was 1,3-dimethyl-2-imidazolidinone Zm-cresol = 5 1.35% by weight 48.65% by weight (1: 1 by molar ratio). Example B 5

100 g of the main fraction obtained in Example B4 was charged into a flask equipped with a cooling pipe and a distillate receiver, and the mixture was boiled at normal pressure under a nitrogen atmosphere. Collected. The recovered liquid was further boiled and recovered in the same manner. The composition of the obtained liquid was 1,3-dimethyl-2-imidazolidinone Z _m -cresol = 5.35% by weight: 48.65% by weight (1: 1 by molar ratio). Example B 6

P-cresol (special grade) was rectified in the same manner as in Example B1, and purified P-cresol having a boiling point of 201.9 and a water content of 10 ppm or less was prepared.

In a dry box, slowly add P-cresol 108.1 (l.OOmol) made from purified 1,3-dimethyl-2-imidazoli prepared in Example B 1 to obtain purified 1,3-dimethyl-2. -Didinone 11.1 g (l.OOmol) was charged into the flask and stirred to obtain an equimolar composition (liquid) of purified midazolidinone and purified P-cresol.

The obtained equimolar composition was heated at normal pressure, and the temperatures of the liquid phase and the gaseous phase at the time of boiling were 236. This is about 11 higher than the boiling point of purified 1,3-dimethyl-2-imidazolidinone (at 225.5) and about 34 higher than the boiling point of purified P-cresol (at 201.9). Met. Further, the obtained equimolar composition was placed in a flask and exposed to ice water at 0 for 3 hours, but the equimolar composition did not solidify and remained in a liquid state.

In addition, 5 g of the obtained equimolar composition was mixed with 5 g of pure water in a sample bottle and stirred vigorously, but the equimolar composition and pure water were not mixed and remained in two layers. Was. Example B 7 The phenol (special grade) was rectified in the same manner as in Example B1 to prepare a purified phenol having a boiling point of 181.2 and a water content of 10 ppm or less.

In a dry box, 14.1 g (l.OOmol) of the purified 1,3-dimethyl-2-imidazolidinone prepared in Example B 1 was charged into a flask, and the mixture was stirred. 4.1 g (l.OOmol) was gradually added to obtain an equimolar composition (liquid) of purified 1,3-dimethyl-2-imidazolidinone and purified phenol.

The obtained equimolar composition was heated at normal pressure, and the temperatures of the liquid phase and the gaseous phase at the time of boiling were measured. It is about 4 higher than the boiling point of purified 1,3-dimethyl-2-imidazolidinone (at 225.5) and about 27 higher than the boiling point of purified P-cresol (at 201.9). Temperature. The obtained equimolar composition was placed in a flask and exposed to ice water of 0 for 3 hours, but the equimolar composition did not solidify and remained in a liquid state.

In addition, 5 g of the obtained equimolar composition was mixed with 5 g of pure water in a sample bottle and stirred vigorously, but the equimolar composition and pure water were not mixed and remained in two layers. Was. Example B 8

P-cloguchi phenol (special grade) was rectified in the same manner as in Example B1 to prepare purified P-cloguchi phenol having a boiling point of 21 ° C and a water content of 10 ppm or less.

In a dry box, 14.1 g (l.OOmol) of the purified 1,3-dimethyl-2-imidazolidinone prepared in Example B 1 was charged into a flask, and while stirring, the purified P- 18.6 g (l.OOmol) of Cloguchi phenol was gradually added to obtain an equimolar composition (liquid) of purified 1,3-dimethyl-2-imidazolidinone and purified P-cloguchiphenol. .

The obtained equimolar composition was heated at normal pressure, and the temperatures of the liquid phase and the gaseous phase during boiling were measured. This is about 32 higher than the boiling point of purified 1,3-dimethyl-2-imidazolidinone (at 25.5) and 40 higher than the boiling point of purified P-chlorophenol (at 21.7). Met. Further, the obtained equimolar composition was placed in a flask and exposed to ice water at 0 for 3 hours, but the equimolar composition did not solidify and remained in a liquid state. Fig. B4 shows the obtained equimolar composition and the IR spectrum of the reagent grade 1,3-dimethyl-2-imidazolidinone and P-chloromouth phenol. Compared to 1,3-dimethyl-2-imidazolidinone and P-chlorophenol alone, the IR spectrum of the equimolar composition shows ΔH stretching vibration that forms intramolecular and intermolecular hydrogen bonds. 3 0 0 0~ 4 0 0 0 cm- 1 6 9 3 cm- 1 band indicating ¹ of broadband and C = 0 stretching vibration is low wavenumber shift. The above results show that in the equimolar composition, C = の of 1,3-dimethyl-2-imidazolidinone and OH of P-chlorophenol form strong hydrogen bonds.

FIGS. B5 and B6 show the ¹ H- and ' ³ C-NMR spectrum of the obtained equimolar composition. The proton and carbon signals of the equimolar composition are equivalent to those of the well-known 1,3-dimethyl-2-imidazolidinone and P-chlorophenol alone, indicating that no ionic bond has been formed.

The obtained equimolar composition had a dielectric constant of 32.5 and a dielectric loss tangent of 0.495. In addition, 5 g of the obtained equimolar composition was mixed with 5 g of pure water in a sample bottle and stirred vigorously, but the equimolar composition and pure water were not mixed and remained in two layers. . Example B 9 to 11

Equimolar composition of purified 1,3-dimethyl-2-imidazolidinone and purified 1,3-dimethyl-2-imidazolidinone obtained in Example B 1 and purified 1,3-dimethyl-2-imidazolidinone or purified P-cloth phenol was blended in the amounts shown in Table B1. Table B1 shows the boiling points measured in the same manner as in Example B1.

Each of the obtained solutions in Table B1 was placed in a flask and exposed to ice water at 0 for 3 hours, but the solution did not solidify and remained in a liquid state. Comparative Example B 1, 2

An equimolar composition of purified 1,3-dimethyl-2-imidazolidinone and purified p-chlorophenol obtained in Example B 1 and purified 1,3-dimethyl-2-imidazolidinone or purified P -Black phenol was blended in the amounts shown in Table B1. Table B1 shows the boiling points measured in the same manner as in Example B1. Table B

Equimolar composition: Equimolar composition of purified 1,3-dimethyl-2-imida V-linenone and purified P-kappa file Content: Equimolar composition amount (g) / mixing amount Total (25g) X 100 (wt%)

Example C 1-9, Comparative Example C 1-9

In a container equipped with a stirrer, reflux condenser, water separator, and nitrogen inlet tube, 799 g of the solvent having the composition shown in Table C1 (the amount of solvent was 2570 g only for Comparative Example C9) and the raw material of polyimide Monomer,

(1) 1,3-bis (4-aminophenoxy) benzene,

146.17 g (0.500 mol),

(2) 3, 3 ', 4, 4'—biphenyltetracarboxylic dianhydride,

143.43 g (0.4875 mol)

(3) anhydride,

3.703 g (25.00 mmol)

, And the mixture was heated from room temperature to 200 over 2 hours and 30 minutes with stirring under a nitrogen atmosphere, and reacted at 200 for 12 hours. In this case, the theoretical yield of the polymer was 275.3 g, and the polymer concentration was 25.6% (9.7% only for Comparative Example C9).

The state of the reaction solution during the heating process from room temperature to 200 and the reaction process at 20 Ot: is shown in Table C2. However, in Table C2, each symbol indicates the following status.

"SL" ...... Slurry state

"BJ ... Polyimide dissolved

"C": Polyimide is slightly precipitated or slightly dissolved

"D": Polyimide partially solidifies and adheres to walls, agitating springs, etc. In addition, for those in which the reaction solution can be agitated (Examples C1 to C9 and Comparative Example C9), fluoric anhydride 3. A solution of 703 g (25.00 mmol) dissolved in 70 g of each solvent was added dropwise, and the reaction was further carried out at 200 for 6 hours.

Thereafter, the inside of the reaction system was cooled to 30. For Examples C 1 to 9, the obtained precipitate was separated by filtration. In Comparative Example C9, no precipitate was obtained at this stage, and the obtained viscous polymer solution was discharged into 10 liters of toluene with vigorous stirring, and the precipitated polymer was separated by filtration.

Further, for Examples C 1-9, the resulting polymer was mixed with 1 liter of each solvent. Then, it was washed with 1 liter of toluene. In Comparative Example C9, the obtained polymer was washed with 2 L of toluene. The polymer thus obtained was pre-dried at 50 for 24 hours and then dried at 300 under a nitrogen stream at 12 hours.

For Examples C1 to C9 and Comparative Example C9, the logarithmic viscosity, glass transition temperature, 5% weight loss temperature, and melt viscosity (430 minutes for 5 minutes) of the obtained polyimide powder were measured by the methods described above. The results obtained are shown in Table C3.

As can be seen from Examples C 1 to 9, when the solvent according to the present invention is used, it is not feasible with a normal solvent system as shown in Comparative Example C (Comparative Example C 2, 4, 6, or 8). The polyimide can be sufficiently synthesized even at a high concentration (about 25 wt%), and the polyimide obtained by the method of the present invention can be polymerized at a low concentration in an ordinary solvent system (Comparative Example C9; about 1 wt%). %) Has the same physical properties as the polyimide obtained by Further, according to the production method of the present invention, since the reaction system is in a slurry state, the isolation of the polyimide can be performed only by filtration, which is a simple process. Also, compared to polyimide obtained by a usual method, physical properties are not changed at all, and good heat resistance is maintained.

Table C I

Table C 2

/ s says not. ^ / Dish 50 ° C 100 ° C 150 ° C 200 ° C

Time 0 hours 3 hours 6 hours 9 hours 12 hours \ c 1 SL SL B C SL SL SL SL SL

H »JC 2 SL SL B C SL SL SL SL SL

H »JC 3 SL SL B SL SL SL SL SL SL t 瞧 C 1 SL SL SL D D ίΙΤ 丰 Hit.

Jt ^, JC 2 SL SL SL B Stirring became difficult.

\ c 4 SL SL B C SL SL SL SL SL

H »JC 5 SL SL BC SL SL SL SL SL i ±» JC 3 SL SL BB Rapidly precipitates at around 180 ° C jt ^ yc 4 SL SL BB Rapidly precipitates at around 190 ° C m ^ \ c 6 SL SL BC SL SL SL SL SL ic 7 SL SL BC SL SL SL SL SL

J: 瞧 C 5 SL SL SL D D D ίΙίίΗϋ i: 瞧 C 6 SL SL SL B Stirring became difficult, mi,

H »JC 8 SL SL B C SL SL SL SL SL

H »JC 9 SL SL B C SL SL SL SL SL

J: congress C 7 SL SL B B 190. Precipitated solid rapidly around C

8 SL SL BB Near 200 ° Ci, "precipitate on Si 敫" i: Kuni C 9 SL SL SL BBB Β Β Β

Table D3

Example C10 ~: I2, Comparative example C10, 1 1

In a vessel equipped with a stirrer, reflux condenser, water separator, and nitrogen inlet tube, 2437 g of a solvent having the composition shown in Table C4,

(1) 4, 4'-bis (3-aminophenoxy) biphenyl,

368.43 g (1.000 mol),

(2) pyromellitic dianhydride,

102.52 g (0.470 mol),

(3) 3, 3 ', 4, 4'—biphenyltetracarboxylic dianhydride,

138.28 g (0.470 mol),

(4) phthalic anhydride,

17.77 g (120.0 mmol)

, And the mixture was heated from room temperature to 200 over 2 hours and 30 minutes with stirring under a nitrogen atmosphere, and reacted at 200 for 4 hours. In this case, the theoretical yield of the polymer was 591.0 g, and the polymer concentration was 19.5%. Table C5 shows the state of the reaction solution during the heating process from room temperature to 200 and the reaction process at 20. However, in Table C5, each symbol indicates the following status.

"SL" ... Polyimide precipitates and the reaction solution is in a slurry state

“B” …… Polyimide dissolves

"C": Polyimide is slightly precipitated or slightly dissolved

“D” …… Polyimide is partially solidified and adheres to wall surfaces, stirring springs, etc.

Further, for those in which the reaction solution can be stirred (Examples C10 to C12, Comparative Example C10), 17.77 g (120. Ommol) of fluoric anhydride was charged, and the mixture was further stirred at 200 for 4 hours. The reaction was performed.

Thereafter, the mixture was cooled to 30 and the resulting precipitates of Examples C 10 to 12 were separated by filtration. In Comparative Example C10, no precipitate was obtained at this stage, and the resulting viscous polymer solution was discharged into 10 liters of toluene with vigorous stirring, and the precipitated polymer was separated by filtration.

Further, for Examples C 10 to 12, the obtained polymer was washed with 1 liter of each solvent and subsequently with 1 liter of toluene. For Comparative Example C10 The obtained polymer was washed with 2 liters of toluene. The polymer thus obtained was pre-dried at 50: for 24 hours, and then dried under reduced pressure at 200 for 12 hours under a nitrogen stream.

For Examples C10 to C12 and Comparative Example C10, the logarithmic viscosity, glass transition temperature, and 5% weight loss temperature of the obtained polyimide powder were measured by the methods described above. The results obtained are shown in Table C6.

Table C4

Table C6

From the results of Examples C1 to C12, according to the production method of the present invention, since the reaction system is in a slurry state, isolation of the polyimide can be performed only by filtration, which is a simple process. . In addition, compared to polyimide obtained by a usual method, physical properties are not changed at all and good heat resistance is maintained. Example C 1 3

In Example C10, instead of the initial charge of phthalic anhydride and the further charge of hydrofluoric anhydride in the stirrable reaction solution, 10.66 g (72. Polyimide was obtained under the same conditions as in Example C10, except that the composition was changed to 1 Ommol) and 41.9-phenylethynylphthalic anhydride 11.92 g (48.00.0 mmol). . The glass transition temperature of the obtained polyimide powder was 238. This powder was further melted in a 360 ° furnace and kept for 4 hours to obtain a bulk polyimide. The glass transition temperature of this polyimide was 246.

Example D 1-9, Comparative Example D 1-9

In a vessel equipped with a stirrer, reflux condenser, water separator, and nitrogen inlet tube, 799 g of the solvent having the composition shown in Table D1 (the amount of solvent was 2570 g for Comparative Example D9 only) ,

(1) 1,3-bis (4-aminophenoxy) benzene,

146.17 g (0.500 mol),

(2) 3,3 ', 4,4, -biphenyltetracarboxylic dianhydride,

143.43 g (0.4875 mol)

(3) anhydride,

3.703 g (25.00 mmol)

The mixture was heated from room temperature to 200 over 2 hours and 30 minutes with stirring under a nitrogen atmosphere, and reacted at 200 for 12 hours. In this case, the theoretical yield of the polymer was 275.3 g, and the polymer concentration was 25.6% (9.7% only for Comparative Example D9).

Table D2 shows the state of the reaction solution during the heating process from room temperature to 200 and the reaction process at 200. However, in Table D2, each symbol indicates the following status.

"SL" ...... Slurry state

“B” …… Polyimide dissolves

"C": Polyimide is slightly precipitated or slightly dissolved

Furthermore, for those in which the reaction solution can be stirred (Examples D1-9 and Comparative Example D9), 3.703 g (25.0 Ommol) of hydrofluoric anhydride was dissolved in 70 g of each solvent. The dissolved solution was added dropwise, and the reaction was further performed at 200 at 6 hours.

Thereafter, the inside of the reaction system was cooled to 3 Ot, and for Examples D 1 to 9, the obtained precipitates were separated by filtration. In Comparative Example D9, no precipitate was obtained at this stage, and the obtained viscous polymer solution was discharged into 10 liters of toluene with vigorous stirring, and the precipitated polymer was separated by filtration.

Further, for Examples D 1 to 9, the obtained polymer was washed with 1 liter of each solvent and subsequently with 1 liter of toluene. Also, Comparative Example D 7 was not obtained. The polymer obtained was washed with 2 liters of toluene. The polymer thus obtained was pre-dried at 50 for 24 hours and then dried at 300 for 12 hours under a stream of nitrogen.

For Examples D1 to D9 and Comparative Example D9, the logarithmic viscosity, glass transition temperature, 5% weight loss temperature, and melt viscosity (430 t: Z5 minutes) of the obtained polyimide powder were measured by the methods described above. The results obtained are shown in Table D4.

As can be seen from Examples D 1 to 9, when the solvent according to the present invention was used, it was not feasible with a normal solvent system as shown in Comparative Example D (Comparative Example D 2, 4, 6, or 8). Polyimide can be sufficiently synthesized even at a high concentration (25 wt%), and the polyimide obtained by the method of the present invention can be obtained by low-concentration polymerization in a normal solvent system (Comparative Example D 9; 1% by weight). It has the same physical properties as the polyimide obtained.

Further, according to the production method of the present invention, since the reaction system is in a slurry state, the isolation of the polyimide can be performed only by filtration, which is a simple process. Also, compared to polyimide obtained by a usual method, physical properties are not changed at all, and good heat resistance is maintained.

Table D1

Table D2

Table D3

Example D 10-; 12, Comparative Example D 10, 1 1

A vessel equipped with a stirrer, reflux condenser, water separator, and nitrogen inlet tube was charged with 2437 g of a solvent having the composition shown in Table D4.

(1) 4,4'-bis (3-aminophenoxy) biphenyl,

368.43 g (1.000 mol),

(2) pyromellitic dianhydride,

102.52 g (0.470 mol),

(3) 3,3 ', 4,4, -biphenyltetracarboxylic dianhydride,

138.28 g (0.470 mol),

(4) phthalic anhydride,

17.77 g (120.0 mmol)

, And the mixture was heated from room temperature to 200 over 2 hours and 30 minutes with stirring under a nitrogen atmosphere, and reacted at 200 for 4 hours. In this case, the theoretical yield of the polymer was 591.0 g, and the polymer concentration was 19.5%. Table D5 shows the state of the reaction solution during the heating process from room temperature to 200 and the reaction process at 200. However, in Table D5, each symbol indicates the following status.

rSLj ...... Polyimide precipitates and the reaction solution is in a slurry state

“B” …… Polyimide dissolves

"C": Polyimide is slightly precipitated or slightly dissolved

Further, for those in which the reaction solution can be stirred (Examples D 10 to 12 and Comparative Example D 10), 17.77 g (120. Ommol) of phthalic anhydride was charged, and the reaction was further carried out at 200 for 4 hours. went.

Thereafter, the inside of the reaction system was cooled to 30. For Examples D 10 to 12, the obtained precipitate was separated by filtration. In Comparative Example D10, no precipitate was obtained at this stage, and the obtained viscous polymer solution was discharged into 10 liters of toluene with vigorous stirring, and the precipitated polymer was separated by filtration.

Further, for Examples D 10 to 12, the obtained polymer was washed with 1 liter of each solvent and subsequently with 1 liter of toluene. For Comparative Example D10 The obtained polymer was washed with 2 liters of toluene. The polymer thus obtained was pre-dried for 50 to 24 hours, and then dried under a nitrogen stream at 200 ° C. for 12 hours under reduced pressure.

For Examples D 10 to 12 and Comparative Example D 10, the logarithmic viscosity, glass transition temperature, and 5% weight loss temperature of the obtained polyimide powder were measured by the methods described above. The results obtained are shown in Table D6.

Table D4

Table D6

From these results, according to the production method of the present invention, since the reaction system is in a slurry state, isolation of the polyimide can be performed only by filtration, which is a simple process. In addition, compared to polyimide obtained by a usual method, physical properties are not changed at all and good heat resistance is maintained. Example D 1 3

In Example D10, instead of the originally charged anhydrous anhydride and further added anhydrous acid to the stirrable reaction solution, 10.66 g (7. 2.0 mmol) and 1.1-92 g (4.80 mmol) of 4-phenylethynylphthalic anhydride were obtained in the same manner as in Example D10. Was. The glass transition temperature of the obtained polyimide powder was 238. The powder was further melted in a furnace at 360 and kept for 4 hours to obtain a lump polyimide. The glass transition temperature of this polyimide was 245.

Example E 1, 2, Comparative example E 1— 12

The reaction was carried out according to Example C1, except that 1031 g of the solvent having the composition shown in Table E1 was used. However, for Comparative Example E5-8, the reaction was carried out at the boiling point of the solvent (180-200 :) under the reflux of the solvent. In this case, the theoretical yield of the polymer was 275.3 g, and the polymer concentration was 21.1%.

Table E2 shows the state of the reaction solution during the heating process and the reaction process from room temperature to the reaction temperature. However, in Table E2, each symbol indicates the following status.

"SL" ...... Slurry state

“B” …… Polyimide dissolves

"C": Polyimide is slightly precipitated or slightly dissolved

"DJ ...... Polyimide is partially solidified and adheres to wall surfaces, stirring springs, etc.

Furthermore, for those in which the reaction solution can be stirred (Examples El and 2, Comparative Examples E 3, 4, 8, and 10), 3.703 g (25.O Ommol) of fluoric anhydride was dissolved in each solution. A solution dissolved in 70 g of the medium was added dropwise, and the reaction was further performed at 200 ° C for 6 hours. Thereafter, the reaction system was cooled to 3 Ot :, and the precipitate was separated by filtration and washed with 1 liter of each solvent and subsequently with 1 liter of toluene. The polymer thus obtained was pre-dried at 50 for 24 hours and then dried at 300 under nitrogen for 12 hours. The logarithmic viscosity, glass transition temperature, 5% weight loss temperature, and melt viscosity (430 °: 5 minutes) of the obtained polyimide powder were measured by the methods described above. Table 4 shows the obtained results.

Comparative Example E As can be seen from 1, 2, 5 to 7, 9, 11, 11 and 12, when a monomer and / or polyimide precursor is dissolved using a solvent containing no equimolar composition and the solution becomes homogeneous. During the reaction, as the imidization proceeds, the reaction solution rapidly becomes jelly-like or solidifies due to the precipitate. In addition, as can be seen from Comparative Examples 3, 4, 8, and 10, when a solvent containing no equimolar composition was used and the monomer and / or the polyimide precursor did not dissolve and the reaction proceeded in a slurry state, The polymerization degree (logarithmic viscosity) of the obtained polyimide is abnormally high, and the thermal stability (weight loss temperature) and the melt fluidity (melt viscosity) are extremely poor. Table El

Equimolar composition: Equimolar composition of nitrogen-containing cyclic compound and phenols Content: Equimolar composition amount (g) Total Z content (g) X 100 (wt%)

Table E2

*: 200 ~ 180 ° C for J g ^ jE5 ~ 8

Table E3

Says logarithmic viscosity glass transition 5% weight loss viscosity [Pa · sec.]

[dl / g] / mux. [° C] / jmJ¾t [° C] (430. C for 5 minutes)

0.93 1 92 562 680

H »JE 2 0.92 1 92 562 650 t 瞧 E 3 1.10 1 96 547 3240

J: Country E 4 1.65 1 98 524 1 5600 t 瞧 E 8 1.58 1 96 550

1: 瞧 E 10 1.85 1 95 544 i§ i¾rti

Example E 4-7, Comparative example E 13--15, Reference example 1

The reaction was carried out according to Example C10 except that 1098 g of the solvent having the composition shown in Table E4 was used. In this case, the theoretical yield of the polymer was 591.0 g, and the polymer concentration was 35.0%.

Table E5 shows the state of the reaction solution during the heating process and the reaction process from room temperature to the reaction temperature. However, in Table E5, each symbol indicates the following status.

"SL" ...... Slurry state

“B” …… Polyimide dissolves

"C": Polyimide is slightly precipitated or slightly dissolved

Further, for those in which the reaction solution can be stirred (Examples E4 to E7), 17.77 g (120.0 mmol) of phthalic anhydride was charged, and the reaction was further performed at 200 for 4 hours. .

Thereafter, the inside of the reaction system was cooled to 30 and the precipitate was separated by filtration and washed with 1 liter of each solvent and subsequently with 1 liter of toluene. The polymer thus obtained was pre-dried for 50 hours and 24 hours, and then dried at 200 ° C. for 12 hours under a nitrogen stream. The logarithmic viscosity, glass transition temperature, 5% weight loss temperature, and melt viscosity (420/5 min) of the obtained polyimide powder were measured by the methods described above. The results obtained are shown in Table E4.

As can be seen from Examples E 4 to 7, when the content of the equimolar composition in the solvent used is high, the polyimide can be sufficiently synthesized even under extremely high concentration conditions such as a polymer concentration of about 35 wt%. Moreover, the obtained polyimide has good physical properties. Table E4

Equimolar composition: equimolar composition of nitrogen-containing cyclic compound and phenols Content: equimolar composition amount (g) Total Z content (g) X 100 (wt%) Table E5

Table E6

Example E 8 9

The reaction temperature was 200 in Example E8 and 230 in Example E9, and a polyimide was synthesized according to Example 10. A portion of the reaction slurry was collected 3, 6, and 9 hours after the start of the reaction, filtered, and dried, and the logarithmic viscosity of the obtained sample was measured. The results are shown in Table E7.

As can be seen from the results, it is possible to shorten the reaction time by increasing the reaction temperature to 200.

Example E 8 {200} Example E 9 5 ^ 12 301 Reaction time (hrs) 3 6 9 3 6 9 Logarithmic viscosity (dl / g) 0.37 0.39 0.40 0.40 0.40 0.40

Example E 10-13, Comparative example E 17-26, Reference example E 2

In a vessel equipped with a stirrer, reflux condenser, water separator, and nitrogen inlet tube, the solvent and the raw materials for polyimide shown in Table E8 are charged, and the mixture is stirred for 2 hours and 30 minutes under a nitrogen atmosphere. Then, the temperature was raised from room temperature to 200, and the reaction was performed at 200 for 4 hours. The polymer concentration during this polymerization was 25.0%.

Table E9 shows the state of the reaction solution during the heating process from room temperature to 200 and the reaction process at 200.

Further, 17.77 g (12.0 mmol) of fluoric anhydride was charged, and the reaction was further carried out at 200 at 4 hours.

Thereafter, the reaction system was cooled to 30 and the precipitate was separated by filtration and washed with 1 liter of solvent and 1 liter of toluene. In Comparative Examples E 19, 21, 23, and 25, no precipitate was obtained at this stage, and the viscous polymer solution was discharged into 10 liters of toluene with vigorous stirring, and the precipitated polymer was collected. The mixture was separated by filtration and washed with 2 liters of toluene. The polymer thus obtained was pre-dried at 50 for 24 hours and then dried under reduced pressure at 200 at 12 hours under a nitrogen stream.

For Examples E 10 to 13 and Comparative Examples E 17, 19, 21, 23, and 25, the logarithmic viscosity and glass transition temperature of the obtained polyimide powder were measured by the above-described methods. The results obtained are shown in Table E9.

驟 QA:>

* 8E Table E9

BAB: 4,4'-bis (3-aminophenoxy) biphenyl BPDA: 3,3'.4,4'-biphenyl ditracarboxylic dianhydride

PMDA: pyromellitic dianhydride PA: phthalic anhydride

Equimolar composition: equimolar composition of m, p "mixed cresol and N-methyl-2-pyrrolidone

Based on the results of Comparative Example El7 and Reference Example E2, the polyimide using pyromellitic dianhydride as the tetracarboxylic dianhydride shows that when the equimolar composition is used as the solvent, Precipitates and solidifies the reaction solution, which is not preferable. In addition, when cresol is used as a solvent, the polyimide precipitates with the progress of imidation and becomes a good slurry state.

On the other hand, a polyimide containing 30 mol% or more of biphenyltetracarboxylic dianhydride as a tetracarboxylic dianhydride, when cresol is used as a solvent, the polyimide is precipitated even if imidization proceeds. For this reason, a large amount of a poor solvent is required to recover the polymer. However, when an equimolar composition is used as the solvent, polyimide is precipitated as the imidization proceeds and a good slurry state is obtained.

From these results, according to the method for producing a pyridine dicarboxylic acid type polyimide according to the present invention, the reaction system is in a slurry state, so that isolation of the polyimide can be performed only by filtration, which is a simple process. In addition, compared to polyimide obtained by a usual method, physical properties are not changed at all and good heat resistance is maintained. Example E 14—E 15; Comparative example E 27—E 39; Reference examples 3, 4, and 5

In a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube, the solvent and the raw material for polyimide shown in Table E10 were charged, and the mixture was stirred under a nitrogen atmosphere over 2 hours. The reaction was heated from room temperature to 200 ° C. and heated at 20 O: for 4 hours. The concentration of the polymer at the time of the polymerization was 25.0%.

Table E10 shows the state of the reaction solution in the temperature rising process from room temperature to 200 and in the reaction process at 20.

Based on these results, bis (3,4-dicarboxyphenoxy) ether anhydride and tetratetracarboxylic dianhydride are used as tetracarboxylic dianhydrides. When using 7-ene-2,3,5,6-tetracarboxylic dianhydride, the solvent solubility of the resulting polyimide is too high, and the equimolar composition is used as the solvent. Also, the obtained polyimide does not precipitate.

PA: phthalic anhydride ODPA: bis (3,4-dicarboxyphthalic acid)

8 Ji 0: bicyclo (2 ₁ 2,2) - O click Bok 7 E "2,3,5,6" Tet carboxylic dianhydride

Equimolar composition: equimolar composition of m, p-mixed cresol and N "methyl 2-pyrrolidone

Claims

The scope of the claims

1. In a solvent containing 50 to 100% by weight of an equimolar composition of a nitrogen-containing cyclic compound represented by the following chemical formula (1) and a phenol represented by the following chemical formula (2): Method for producing polyimide by imidation reaction with tetracarboxylic dianhydride

H ₃ C-

(In the formula (l), X represents —CH ₂ — or —N (CH ₃ ) _. In the formula (2), R 1, and R ₂ may be the same or different from each other. , -0H, - C, -C2H7, -CHHT, -C2H9, -CsHiu -CeH.s, - 5, -CsHn, -C9H.9, -C10H2 ,, - 0C, -0 (CeHs), - N ( k-Cl, -Br or -F.)

2. The method for producing a polyimide according to claim 1, wherein the tetracarboxylic dianhydride contains pyridine dicarboxylic acid.

3. The tetracarboxylic dianhydride contains 30 to 100% by mole of biphenyltetracarboxylic dianhydride with respect to all the titracarboxylic dianhydrides. Item 3. The method for producing a polyimide according to Item 1 or 2.

4. The method for producing a polyimide according to any one of claims 1 to 3, wherein the polyimide obtained by the imidation reaction has a repeating structure represented by the following chemical formula (3):

(In Formula (3), Y is represented by at least one selected from the group consisting of Formulas (e) to (h).)

(Where R may be the same or different from each other,

Single bond, one O—, —CO—, -SO2-, —S—, one CH ₂ — or

One of C (CH ₃ ) ₂ —. ).

5. The repeating structure represented by the chemical formula (3) is contained in a proportion of 30 to 100 mol% in all the repeating structures, and the residue different from the repeating structure represented by the chemical formula (3) is 0 to 100 mol%. The method for producing a polyimide according to any one of claims 1 to 4, wherein the polyimide is contained at a ratio of 70 mol%.

6. The remnant has a repeating structure different from the repeating structure represented by the chemical formula (3), and has a repeating structure comprising a component unit derived from an aromatic tetracarboxylic acid. 6. The method for producing a polyimide according to 5.

7. The repeating structure comprising a component unit derived from an aromatic tetracarboxylic acid is a repeating structure represented by the following chemical formulas (a) and Z or (b). A method for producing a polyimide;

(b)

(In the formulas (a) and (b), the formulas (e) to (h)

^(g) In formulas (f), (g) and (h), Rs may be the same or different from each other, and are each a single bond,

One hundred and one, -CO-, _S0 ₂ -, one S-, - CH ₂ - or a C (CH ₃₎ ₂ - shows a noise Zureka.

In the above formula (b), Ar ₂ is at least selected from the group consisting of —〇, —CO—, — S〇 ₂ —, — S—, — CH ₂ — or — C (CH ₃ ) ₂ _ Represented by one. ).

8. The polyimide having a repeating structure represented by the general formula (3) is a polyimide having at least one kind of a repeating structure represented by any of the following general formulas (4) to (6). The method for producing a polyimide according to any one of claims 1 to 7, wherein:

9. The compound according to any one of claims 1 to 8, wherein the compound represented by the chemical formula (1) is N-methyl-2-pyrrolidone and no or 1,3'-dimethyl-2-imidazolidinone. Or a method for producing a polyimide.

0. The phenols represented by the chemical formula (2) are phenol, Phenol, m-chlorophenol, p-chlorophenol, 0-cresol, m-cresol, P-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6- The method for producing a polyimide according to any one of claims 1 to 9, wherein the polyimide is at least one compound selected from the group consisting of xylenol, 3,4-xylenol, and 3,5-xylenol.

11. A solvent containing an equimolar composition of the compound represented by the chemical formula (1) and the phenols represented by the chemical formula (2) in an amount of 50 to 100% by weight, 10. The composition according to claim 1, further comprising a compound represented by the chemical formula (1) or a phenol represented by the chemical formula (2) in an amount of 0 to 50% by weight. The method for producing a polyimide according to any one of the above.

12. The polyimide according to any one of claims 1 to 11, wherein the method for producing a polyimide comprises precipitating the polyimide and / or the oligomer during the imidization reaction to make the reaction system a slurry. Manufacturing method.

13. The method for producing a polyimide according to any one of claims 1 to 12, wherein the reaction is performed in the presence of a terminal blocking agent.

14. A method for producing a polyimide according to the method for producing a polyimide according to any one of claims 1 to 13, wherein a product is precipitated during the imidization reaction to obtain a polyimide powder.

15 5. The concentration of the raw monomer composed of diamines and tetracarboxylic dianhydride in the reaction solution ((total weight of raw monomers) / (total weight of raw monomers + weight of solvent)) is 5 Claims: in the range of up to 50% by weight.

;! 15. The method for producing a polyimide according to any one of items 14 to 14.

16. A polyimide obtained by the method according to any one of claims 1 to 15.

1 7. A polyimide powder obtained by the method according to any one of claims 1 to 15. H

1 8. A solvent comprising an equimolar composition of a compound represented by the following chemical formula (1) and a phenol represented by the following chemical formula (2):

In Formula (U), X represents —CH ₂ — or one N (CH ₃ ) _. Wherein (2), R ,, R2, which may be the same or different from each other, respectively, - H, -OH, - CH 3, - H 7 ,, - C 2 ,, - -? C H _{, - C -CsH.9, -C.oH 2 u} - OCIk - 0 (C 6 H 5), - NO -Cl, - indicate either Br or _F. ).

19. The solvent according to claim 18, comprising 50 to 100% by weight of an equimolar composition of the compound represented by the chemical formula (1) and the phenols represented by the chemical formula (2). .